U.S. patent application number 13/318978 was filed with the patent office on 2012-11-22 for insecticidal compounds.
This patent application is currently assigned to SYNGENTA CROP PROTECTION, LLC. Invention is credited to Christopher Richard Ayles Godfrey, Ottmar Franz Hueter, Pierre Joseph Marcel Jung, Peter Maienfisch, Peter Renold.
Application Number | 20120295907 13/318978 |
Document ID | / |
Family ID | 42355420 |
Filed Date | 2012-11-22 |
United States Patent
Application |
20120295907 |
Kind Code |
A1 |
Maienfisch; Peter ; et
al. |
November 22, 2012 |
INSECTICIDAL COMPOUNDS
Abstract
The present invention relates to bis-amide derivatives of
formula (I), to processes and intermediates for preparing them, to
methods of using them to control insect, acarine, nematode and
mollusc pests, and to insecticidal, acaricidal, nematicidal and
molluscicidal compositions comprising them. ##STR00001##
Inventors: |
Maienfisch; Peter; (Stein,
CH) ; Godfrey; Christopher Richard Ayles; (Stein,
CH) ; Jung; Pierre Joseph Marcel; (Stein, CH)
; Hueter; Ottmar Franz; (Stein, CH) ; Renold;
Peter; (Stein, CH) |
Assignee: |
SYNGENTA CROP PROTECTION,
LLC
Greensboro
NC
|
Family ID: |
42355420 |
Appl. No.: |
13/318978 |
Filed: |
April 14, 2010 |
PCT Filed: |
April 14, 2010 |
PCT NO: |
PCT/EP2010/054864 |
371 Date: |
January 23, 2012 |
Current U.S.
Class: |
514/235.8 ;
514/256; 514/355; 514/522; 514/616; 544/120; 544/335; 546/316;
558/415; 564/158 |
Current CPC
Class: |
C07C 317/44 20130101;
C07D 275/03 20130101; C07D 213/81 20130101; C07D 277/56 20130101;
C07D 213/64 20130101; C07D 285/06 20130101; A01N 43/76 20130101;
A01N 43/60 20130101; A01N 43/54 20130101; A01N 43/32 20130101; C07C
237/44 20130101; C07D 241/24 20130101; A01N 43/36 20130101; C07D
313/10 20130101; C07D 239/30 20130101; C07D 261/12 20130101; C07D
231/16 20130101; A01N 37/46 20130101; C07D 307/56 20130101; A01N
43/78 20130101; C07C 323/62 20130101; C07D 241/26 20130101; C07D
261/10 20130101; C07D 207/34 20130101; C07C 255/57 20130101; C07D
333/28 20130101; A01N 43/08 20130101; A01N 43/80 20130101; A01N
43/40 20130101; C07D 213/61 20130101; C07D 213/60 20130101; C07D
213/70 20130101; C07D 213/89 20130101; A01N 43/10 20130101; C07D
307/72 20130101; C07D 239/28 20130101; C07D 263/34 20130101; C07D
333/38 20130101; C07D 307/36 20130101; A01N 43/24 20130101; C07D
307/68 20130101; A01N 43/56 20130101; C07C 317/46 20130101; C07D
231/14 20130101; A01N 43/82 20130101 |
Class at
Publication: |
514/235.8 ;
564/158; 514/616; 558/415; 514/522; 546/316; 514/355; 544/335;
514/256; 544/120 |
International
Class: |
C07C 233/76 20060101
C07C233/76; C07C 255/59 20060101 C07C255/59; A01N 37/34 20060101
A01N037/34; C07D 213/82 20060101 C07D213/82; A01N 43/40 20060101
A01N043/40; A01P 9/00 20060101 A01P009/00; A01N 43/54 20060101
A01N043/54; C07D 413/04 20060101 C07D413/04; A01N 43/84 20060101
A01N043/84; A01P 7/04 20060101 A01P007/04; A01P 7/02 20060101
A01P007/02; A01P 5/00 20060101 A01P005/00; A01N 37/24 20060101
A01N037/24; C07D 239/28 20060101 C07D239/28 |
Foreign Application Data
Date |
Code |
Application Number |
May 6, 2009 |
GB |
0907824.7 |
Jan 15, 2010 |
EP |
10150814.1 |
Claims
1. A compound of formula (I) ##STR00038## wherein Q.sup.1 is aryl
or heterocyclyl, each optionally substituted by one to five R.sup.3
substituents, which may be the same or different; Q.sup.2 is
selected from 2-ethyl-6-methyl-4-(nonafluorobut-2-yl)phenyl,
2-bromo-6-chloro-4-(nonafluorobut-2-yl)phenyl,
2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl,
2,6-dimethyl-4-(nonafluoro-but-2-yl)phenyl,
2-chloro-6-methoxymethyl-4-(nonafluorobut-2-yl)phenyl, and
2-bromo-6-methoxymethyl-4-(nonafluorobut-2-yl)phenyl; R.sup.1 is
selected from hydrogen, C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkylcarbonyl, C.sub.1-C.sub.8alkoxycarbonyl and
C.sub.1-C.sub.4alkyl-C(O)NH.sub.2; R.sup.2 is selected from
hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylcarbonyl,
C.sub.1-C.sub.8alkoxycarbonyl and
C.sub.1-C.sub.4alkyl-C(O)NH.sub.2; and R.sup.3 is selected from
cyano, nitro, halogen, hydroxyl, acetoxy, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy,
CN--C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkyl-C(O)O,
C.sub.1-C.sub.4alkyl-S(O).sub.2, NH.sub.2, C.sub.1-C.sub.4alkylNH,
(C.sub.1-C.sub.4alkyl).sub.2N, (C.sub.1-C.sub.4alkylO).sub.2P(O)O,
phenyl and a five to six-membered monocyclic heterocycle containing
1 to 3 heteroatoms independently selected from nitrogen, oxygen and
sulfur; or an agrochemically acceptable salt or N-oxides
thereof.
2. A compound according to claim 1 wherein Q.sup.1 is selected from
phenyl, biphenyl and a five to six-membered monocyclic heteroaryl
group containing 1, 2 or 3 heteroatoms independently selected from
nitrogen, oxygen and sulfur; each optionally substituted by one to
five R.sup.3 substituents, which may be the same or different.
3. A compound according to claim 2 wherein Q.sup.1 is selected from
phenyl, biphenyl, furanyl, pyridyl, thienyl, thiadiazolyl,
oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl and
pyrimidinyl; each optionally substituted by one to three R.sup.3
substituents, which may be the same or different.
4. A compound according to claim 1 wherein R.sup.3 is selected from
cyano, nitro, fluoro, chloro, bromo, iodo, hydroxyl, acetoxy,
methyl, ethyl, isopropyl, tert-butyl, difluoromethyl,
trifluoromethyl, methoxy, ethoxy, difluoromethoxy,
trifluoromethoxy, methylthio, isopropylthio, 3-ethoxy-n-propyl,
methoxymethyl, 2-methoxyethoxy, CH.sub.2CN, C(O)OCH.sub.3,
S(O).sub.2CH.sub.3, NH.sub.2, N(CH.sub.3).sub.2,
OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl, N-pyrroyl, thiadiazolyl, and
pyridyl.
5. A compound according to claim 4 wherein R.sup.3 is selected
cyano, nitro, bromo, chloro, fluoro, methyl, ethyl,
trifluoromethyl, methoxy and trifluoromethoxy.
6. A compound according to claim 1 wherein R.sup.1 and R.sup.2 are
both hydrogen.
7. A compound according to claim 1 wherein Q.sup.2 is selected from
2-ethyl-6-methyl-4-(nonafluoro-but-2-yl)phenyl,
2-bromo-6-chloro-4-(nonafluoro-but-2-yl)phenyl, and
2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl.
8. A compound of formula (II) ##STR00039## wherein Q.sup.1 is as
defined in claim 1; R.sup.1 and R.sup.2 are as defined in claim 1;
R.sup.3 is as defined in claim 1; and Q.sup.2 is selected from:
2-ethyl-6-methyl-4-(perfluoroisopropyl)phenyl,
2-bromo-6-chloro-4-(perfluoroisopropyl)phenyl,
2,6-dichloro-4-(perfluoroisopropyl)phenyl,
2,6-dimethyl-4-(perfluoroisopropyl)phenyl, and
2-methyl-6-methoxymethyl-4-(perfluoroisopropyl)phenyl; or an
agrochemically acceptable salt or N-oxides thereof.
9. A method of controlling insects, acarines, nematodes or molluscs
which comprises applying to a pest, to a locus of a pest, or to a
plant susceptible to attack by a pest an insecticidally,
acaricidally, nematicidally or molluscicidally effective amount of
a compound of formula (I) as defined in claim 1.
10. An insecticidal, acaricidal, nematicidal or molluscicidal
composition comprising an insecticidally, acaricidally,
nematicidally or molluscicidally effective amount of a compound of
formula (I) as defined in claim 1 together with an agrochemically
acceptable diluent or carrier.
11. A composition according to claim 10 which further comprises one
or more additional insecticidal, acaricidal, nematicidal or
molluscicidal compounds.
Description
[0001] The present invention relates to bis-amide derivatives, to
processes and intermediates for preparing them, to methods of using
them to control insect, acarine, nematode and mollusc pests, and to
insecticidal, acaricidal, nematicidal and molluscicidal
compositions comprising them.
[0002] Compounds having insecticidal properties are disclosed in EP
1,714,958, JP 2006/306771, WO 2006/137376, EP 1,916,236, WO
2007/017075, WO 2008/000438, WO 2008/074427 and WO 2009/049845.
There exists a need for alternative methods of control of pests.
Preferably, new compounds may possess improved insecticidal
properties, such as improved efficacy, improved selectivity,
reduced toxicity, lower tendency to generate resistance or activity
against a broader range of pests. Compounds may be more
advantageously formulated or provide more efficient delivery and
retention at sites of action, or may be more readily
biodegradable.
[0003] It has surprisingly been found that certain bisamide
derivatives, which are substituted by an arylperfluorobutyl group,
have beneficial properties, which makes them particularly suitable
for use as insecticides.
[0004] The present invention therefore provides a compound of
formula (I)
##STR00002##
wherein Q.sup.1 is aryl or heterocyclyl, each optionally
substituted by one to five R.sup.3 substituents, which may be the
same or different; Q.sup.2 is selected from [0005]
2-ethyl-6-methyl-4-(nonafluorobut-2-yl)phenyl, [0006]
2-bromo-6-chloro-4-(nonafluorobut-2-yl)phenyl, [0007]
2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl, [0008]
2,6-dimethyl-4-(nonafluoro-but-2-yl)phenyl, [0009]
2-chloro-6-methoxymethyl-4-(nonafluorobut-2-yl)phenyl, and [0010]
2-bromo-6-methoxymethyl-4-(nonafluorobut-2-yl)phenyl; R.sup.1 is
selected from hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
alkylcarbonyl, C.sub.1-C.sub.8 alkoxycarbonyl and
C.sub.1-C.sub.4alkyl-C(O)NH.sub.2; R.sup.2 is selected from
hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkylcarbonyl,
C.sub.1-C.sub.8 alkoxycarbonyl and
C.sub.1-C.sub.4alkyl-C(O)NH.sub.2; and R.sup.3 is selected from
cyano, nitro, halogen, hydroxyl, acetoxy, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy,
CN--C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkyl-C(O)O,
C.sub.1-C.sub.4alkyl-S(O).sub.2, NH.sub.2, C.sub.1-C.sub.4alkylNH,
(C.sub.1-C.sub.4alkyl).sub.2N, (C.sub.1-C.sub.4alkylO).sub.2P(O)O,
phenyl and a five to six-membered monocyclic heterocycle containing
1 to 3 heteroatoms independently selected from nitrogen, oxygen and
sulfur; or an agrochemically acceptable salt or N-oxides
thereof.
[0011] The compounds of formula (I) may exist in different
geometric or optical isomers (enantiomers and/or diasteroisomers)
or tautomeric forms. This invention covers all such isomers and
tautomers and mixtures thereof in all proportions as well as
isotopic forms such as deuterated compounds.
[0012] Unless otherwise indicated, alkyl, on its own or as part of
another group, such as alkoxy, alkylcarbonyl or alkoxycarbonyl, may
be straight or branched chain and may preferably contain from 1 to
6 carbon atoms, more preferably 1 to 4, and most preferably 1 to 3.
Examples of alkyl include methyl, ethyl, n-propyl, iso-propyl,
n-butyl, sec-butyl, iso-butyl and tert-butyl.
[0013] Halogen means fluorine, chlorine, bromine or iodine.
[0014] Haloalkyl groups may contain one or more identical or
different halogen atoms, and includes, for example,
trifluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl or
2,2-difluoroethyl. Perfluoroalkyl groups are alkyl groups which are
completely substituted with fluorine atoms and include, for
example, trifluoromethyl, pentafluoroethyl, heptafluoroprop-2-yl
and nonafluoro-but-2-yl.
[0015] Aryl includes phenyl, naphthyl, anthracenyl, indenyl,
phenanthrenyl and biphenyl, with phenyl being preferred.
[0016] Heteroaryl means a mono-, bi- or tricyclic, aromatic
hydrocarbon, containing 3 to 14, preferably 4 to 10, more
preferably 4 to 7, most preferably 5 to 6 ring-atoms, including 1
to 6, preferably 1 to 4, more preferably, 1, 2 or 3 heteroatoms
independently selected from nitrogen, oxygen and sulfur. Examples
include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl,
isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl,
triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl,
pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothienyl,
benzofuranyl, benzimidazolyl, benzothiadiazolyl, indazolyl,
benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolyl,
isoquinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl
and naphthyridinyl. Preferred, are monocyclic heteroaryl groups
containing 4 to 7, preferably 5 to 6 ring-atoms, including 1, 2 or
3 heteroatoms independently selected from nitrogen, oxygen and
sulfur.
[0017] Heterocyclyl, as used herein, includes heteroaryl, and in
addition may be a saturated or partially unsaturated monocyclic or
bicyclic hydrocarbon containing from 3 to 10 ring-atoms including 1
to 6, preferably 1 to 4, more preferably 1, 2 or 3 heteroatoms
independently selected from nitrogen, oxygen and sulfur. Examples
of non-aromatic heterocyclyl groups are oxiranyl, azetidinyl,
tetrahydrofuranyl, thiolanyl, pyrrolidinyl, pyrrolinyl,
imidazolidinyl, imidazolinyl, sulfolanyl, dioxolanyl,
dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl,
pyrazolidinyl, 1,3-dioxanyl, 1,4-dioxanyl, morpholinyl, dithianyl,
thiomorpholinyl, piperazinyl, azepinyl, oxazepinyl, thiazepinyl,
thiazolinyl, diazapanyl, 2,3-dihydrobenzofuranyl,
3,4-dihydro-2H-benzo[b][1,4]dioxepinyl, benzo[1,3]dioxolanyl and
2,3-dihydrobenzo[1,4]dioxinyl.
[0018] Preferred values of Q.sup.1, Q.sup.2, R.sup.1, R.sup.2 and
R.sup.3 are, in any combination, as set out below.
[0019] Preferably, Q.sup.1 is aryl or heteroaryl; each optionally
substituted by one to five R.sup.3 substituents, which may be the
same or different.
[0020] More preferably, Q.sup.1 is selected from phenyl, biphenyl
and a five to six-membered monocyclic heteroaryl group containing
1, 2 or 3 heteroatoms independently selected from nitrogen, oxygen
and sulfur; each optionally substituted by one to five R.sup.3
substituents, which may be the same or different.
[0021] Yet more preferably, Q.sup.1 is selected from phenyl,
biphenyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl,
thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl,
thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl,
pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl,
benzothienyl, benzofuranyl, benzimidazolyl, benzothiadiazolyl,
indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolyl,
isoquinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl
and naphthyridinyl; each optionally substituted by one to five
R.sup.3, and more preferably by one to three R.sup.3 substituents,
which may be the same or different.
[0022] Even more preferably, Q.sup.1 is selected from phenyl,
biphenyl, furanyl, pyridyl, thienyl, thiadiazolyl, oxazolyl,
isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl and pyrimidinyl;
each optionally substituted by one to three R.sup.3 substituents,
which may be the same or different.
[0023] Preferably, R.sup.3 is selected from cyano, nitro, fluoro,
chloro, bromo, iodo, hydroxyl, acetoxy, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy, CH.sub.2--CN,
C(O)OCH.sub.3, S(O).sub.2CH.sub.3, NH.sub.2, N(CH.sub.3).sub.2,
OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl, N-pyrroyl, thiadiazolyl, and
pyridyl.
[0024] More preferably, R.sup.3 is selected from cyano, nitro,
fluoro, chloro, bromo, iodo, hydroxyl, acetoxy, methyl, ethyl,
isopropyl, tert-butyl, difluoromethyl, trifluoromethyl, methoxy,
ethoxy, difluoromethoxy, trifluoromethoxy, methylthio,
isopropylthio, 3-ethoxy-n-propyl, methoxymethyl, 2-methoxyethoxy,
CH.sub.2CN, C(O)OCH.sub.3, S(O).sub.2CH.sub.3, NH.sub.2,
N(CH.sub.3).sub.2, OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl,
N-pyrroyl, thiadiazolyl, and pyridyl.
[0025] Most preferably, R.sup.3 is selected cyano, nitro, bromo,
chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy and
trifluoromethoxy.
[0026] Most preferred Q.sup.1 are as herein-defined in the examples
and compounds of Tables A to M.
[0027] Preferably, Q.sup.2 is selected from [0028]
2-ethyl-6-methyl-4-(nonafluoro-but-2-yl)phenyl, [0029]
2-bromo-6-chloro-4-(nonafluoro-but-2-yl)phenyl, and [0030]
2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl.
[0031] Preferably, R.sup.1 is hydrogen. Preferably, R.sup.2 is
hydrogen.
[0032] In a first preferred aspect, the present invention provides
a compound of formula (I) wherein Q.sup.2 is
2-ethyl-6-methyl-4-(nonafluoro-but-2-yl)phenyl; and Q.sup.1,
R.sup.1, R.sup.2 and R.sup.3 are defined herein.
[0033] In a preferred embodiment of the first preferred aspect, the
present invention provides a compound of formula (I) wherein
[0034] Q.sup.2 is
2-ethyl-6-methyl-4-(nonafluoro-but-2-yl)phenyl;
[0035] Q.sup.1 is selected from phenyl, biphenyl, furyl, thienyl,
pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl,
pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
tetrazinyl, indolyl, benzothienyl, benzofuranyl, benzimidazolyl,
benzothiadiazolyl, indazolyl, benzotriazolyl, benzothiazolyl,
benzoxazolyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl,
quinazolinyl, cinnolinyl and naphthyridinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0036] R.sup.1 and R.sup.2 are both hydrogen; and
[0037] R.sup.3 is selected from cyano, nitro, fluoro, chloro,
bromo, iodo, hydroxyl, acetoxy, methyl, ethyl, isopropyl,
tert-butyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethoxy, trifluoromethoxy, methylthio, isopropylthio,
3-ethoxy-n-propyl, methoxymethyl, 2-methoxyethoxy, CH.sub.2--CN,
C(O)OCH.sub.3, S(O).sub.2CH.sub.3, NH.sub.2, N(CH.sub.3).sub.2,
OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl, N-pyrroyl, thiadiazolyl, and
pyridyl.
[0038] In a more preferred embodiment of the first preferred
aspect, the present invention provides a compound of formula (I)
wherein
[0039] Q.sup.2 is
2-ethyl-6-methyl-4-(nonafluoro-but-2-yl)phenyl;
[0040] Q.sup.1 is selected from phenyl, biphenyl, furanyl, pyridyl,
thienyl, thiadiazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, pyrazolyl and pyrimidinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0041] R.sup.1 and R.sup.2 are both hydrogen; and
[0042] R.sup.3 is selected cyano, nitro, bromo, chloro, fluoro,
methyl, ethyl, trifluoromethyl, methoxy and trifluoromethoxy.
[0043] In a second preferred aspect, the present invention provides
a compound of formula (I) wherein Q.sup.2 is
2-bromo-6-chloro-4-(nonafluoro-but-2-yl)phenyl; and Q.sup.1,
R.sup.1, R.sup.2 and R.sup.3 are defined herein.
[0044] In a preferred embodiment of the second preferred aspect,
the present invention provides a compound of formula (I)
wherein
[0045] Q.sup.2 is
2-bromo-6-chloro-4-(nonafluoro-but-2-yl)phenyl;
[0046] Q.sup.1 is selected from phenyl, biphenyl, furyl, thienyl,
pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl,
pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
tetrazinyl, indolyl, benzothienyl, benzofuranyl, benzimidazolyl,
benzothiadiazolyl, indazolyl, benzotriazolyl, benzothiazolyl,
benzoxazolyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl,
quinazolinyl, cinnolinyl and naphthyridinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0047] R.sup.1 and R.sup.2 are both hydrogen; and
[0048] R.sup.3 is selected from cyano, nitro, fluoro, chloro,
bromo, iodo, hydroxyl, acetoxy, methyl, ethyl, isopropyl,
tert-butyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethoxy, trifluoromethoxy, methylthio, isopropylthio,
3-ethoxy-n-propyl, methoxymethyl, 2-methoxyethoxy, CH.sub.2--CN,
C(O)OCH.sub.3, S(O).sub.2CH.sub.3, NH.sub.2, N(CH.sub.3).sub.2,
OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl, N-pyrroyl, thiadiazolyl, and
pyridyl.
[0049] In a more preferred embodiment of the second preferred
aspect, the present invention provides a compound of formula (I)
wherein
[0050] Q.sup.2 is
2-bromo-6-chloro-4-(nonafluoro-but-2-yl)phenyl;
[0051] Q.sup.1 is selected from phenyl, biphenyl, furanyl, pyridyl,
thienyl, thiadiazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, pyrazolyl and pyrimidinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0052] R.sup.1 and R.sup.2 are both hydrogen; and
[0053] R.sup.3 is selected cyano, nitro, bromo, chloro, fluoro,
methyl, ethyl, trifluoromethyl, methoxy and trifluoromethoxy.
[0054] In a third preferred aspect, the present invention provides
a compound of formula (I) wherein Q.sup.2 is
2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl; and Q.sup.1, R.sup.1,
R.sup.2 and R.sup.3 are defined wherein.
[0055] In a preferred embodiment of the third preferred aspect, the
present invention provides a compound of formula (I) wherein
[0056] Q.sup.2 is 2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl;
[0057] Q.sup.1 is selected from phenyl, biphenyl, furyl, thienyl,
pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl,
pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
tetrazinyl, indolyl, benzothienyl, benzofuranyl, benzimidazolyl,
benzothiadiazolyl, indazolyl, benzotriazolyl, benzothiazolyl,
benzoxazolyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl,
quinazolinyl, cinnolinyl and naphthyridinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0058] R.sup.1 and R.sup.2 are both hydrogen; and
[0059] R.sup.3 is selected from cyano, nitro, fluoro, chloro,
bromo, iodo, hydroxyl, acetoxy, methyl, ethyl, isopropyl,
tert-butyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethoxy, trifluoromethoxy, methylthio, isopropylthio,
3-ethoxy-n-propyl, methoxymethyl, 2-methoxyethoxy, CH.sub.2--CN,
C(O)OCH.sub.3, S(O).sub.2CH.sub.3, NH.sub.2, N(CH.sub.3).sub.2,
OP(O)(CH.sub.2CH.sub.3).sub.2, phenyl, N-pyrroyl, thiadiazolyl, and
pyridyl.
[0060] In a more preferred embodiment of the third preferred aspect
t, the present invention provides a compound of formula (I)
wherein
[0061] Q.sup.2 is 2,6-dichloro-4-(nonafluoro-but-2-yl)phenyl;
[0062] Q.sup.1 is selected from phenyl, biphenyl, furanyl, pyridyl,
thienyl, thiadiazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, pyrazolyl and pyrimidinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0063] R.sup.1 and R.sup.2 are both hydrogen; and
[0064] R.sup.3 is selected cyano, nitro, bromo, chloro, fluoro,
methyl, ethyl, trifluoromethyl, methoxy and trifluoromethoxy.
[0065] Most preferred compounds of formula (I) are selected from
[0066]
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-ph-
enyl]-3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound
No. A5 of Table A); [0067]
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound
No. A3 of Table A); [0068]
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phe-
nyl]-3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound
No. B2 of Table B); [0069]
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-ph-
enyl]-3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound
No. B1 of Table B); [0070]
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-
-3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound No.
C1 of Table C); [0071]
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]-
-3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound No.
C2 of Table C); [0072]
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-3-(4-fluorobenzoylamino)-2-methoxybenzamide (Compound No. A1
of Table A); [0073]
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-ph-
enyl]-3-(4-cyanobenzoylamino)-2-methoxybenzamide (Compound No. A4
of Table A); [0074]
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-3-(2-methyl-3-nitrobenzoylamino)-2-methoxybenzamide (Compound
No. A2 of Table A); and [0075]
N-{3-[2-Bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-
-phenylcarbamoyl]-2-methoxyphenyl}-2,4,6-trifluorobenzamide
(Compound No. B189 of Table B).
[0076] In an additional aspect the present invention provides a
compound of formula (II),
##STR00003##
[0077] wherein Q.sup.1, R.sup.1, R.sup.2 and R.sup.3 are as defined
for formula (I) and the preferred embodiments thereof correspond to
those of formula (I); and
[0078] Q.sup.2 is selected from:
[0079] 2-ethyl-6-methyl-4-(perfluoroisopropyl)phenyl,
[0080] 2-bromo-6-chloro-4-(perfluoroisopropyl)phenyl,
[0081] 2,6-dichloro-4-(perfluoroisopropyl)phenyl,
[0082] 2,6-dimethyl-4-(perfluoroisopropyl)phenyl, and
[0083] 2-methyl-6-methoxymethyl-4-(perfluoroisopropyl)phenyl.
[0084] In a preferred embodiment, the present invention provides a
compound of formula (II), wherein
[0085] Q.sup.1 is selected from phenyl, biphenyl, furanyl, pyridyl,
thienyl, thiadiazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, pyrazolyl and pyrimidinyl; each optionally
substituted by one to three R.sup.3 substituents, which may be the
same or different;
[0086] R.sup.1 and R.sup.2 are both hydrogen; and
[0087] R.sup.3 is selected cyano, nitro, bromo, chloro, fluoro,
methyl, ethyl, trifluoromethyl, methoxy and trifluoromethoxy;
and
[0088] Q.sup.2 is selected from:
[0089] 2-ethyl-6-methyl-4-(perfluoroisopropyl)phenyl,
[0090] 2-bromo-6-chloro-4-(perfluoroisopropyl)phenyl,
[0091] 2,6-dichloro-4-(perfluoroisopropyl)phenyl,
[0092] 2,6-dimethyl-4-(perfluoroisopropyl)phenyl, and
[0093] 2-methyl-6-methoxymethyl-4-(perfluoroisopropyl)phenyl;
or an agrochemically acceptable salt or N-oxides thereof. Most
preferred compounds of formula (II) are those of Tables E, G, J, K
and L.
[0094] The compounds of the invention may be made by a variety of
methods, for example, the methods disclosed in WO 08/000,438.
[0095] 1) Compounds of formula (I) may be made by treatment of
compounds of formula (V), wherein R is OH, C.sub.1-C.sub.6alkoxy,
Cl, F or Br with an amine of formula NHR.sup.2Q.sup.2. When R is OH
such reactions may be carried out in the presence of a coupling
reagent, such as DCC(N,N'-dicyclohexylcarbodiimide), EDC
(1-ethyl-3-[3-dimethylamino-propyl]carbodiimide hydrochloride) or
BOP-Cl(bis(2-oxo-3-oxazolidinyl)phosphonic chloride), in the
presence of a base, such as pyridine, triethylamine,
4-(dimethylamino)pyridine or diisopropylethylamine, and optionally
in the presence of a nucleophilic catalyst, such as
hydroxybenzotriazole. When R is Cl, such reactions may be carried
out under basic conditions, for example in the presence of
pyridine, triethylamine, 4-(dimethylamino)pyridine or
diisopropylethylamine, and optionally in the presence of a
nucleophilic catalyst. Alternatively, the reaction may be conducted
in a biphasic system comprising an organic solvent, preferably
ethyl acetate, and an aqueous solvent, preferably a solution of
sodium bicarbonate. When R is C.sub.1-C.sub.6alkoxy the ester may
be converted directly to the amide by heating the ester and amine
together in a thermal process.
##STR00004##
[0096] 2) Acid halides of formula (V), wherein R is Cl, F or Br,
may be made from carboxylic acids of formula (V), wherein R is OH
by treatment with thionyl chloride or oxalyl chloride.
[0097] 3) Carboxylic acids of formula (V), wherein R is OH, may be
formed from esters of formula (V), wherein R is
C.sub.1-C.sub.6alkoxy by treatment of the ester with an alkali
hydroxide, such as sodium hydroxide, in a solvent, such as
ethanol.
[0098] 4) Esters of formula (V), wherein R is
C.sub.1-C.sub.6alkoxy, may be made by treatment of compounds of
formula (IV), wherein R is C.sub.1-C.sub.6alkoxy, by acylation with
a carboxylic acid of formula Q.sup.1-COOH or an acid halide of
formula Q.sup.1-COHal, wherein Hal is Cl, F or Br, under standard
conditions as described in 1).
[0099] 5) Compounds of formula (IV), wherein R is
C.sub.1-C.sub.6alkoxy, may be made from compounds of formula (VI)
by sequential treatment with an alcohol R--OH under acidic
conditions and then formation of the N--R.sup.1 bond. For example,
reductive amination may be achieved by treatment of the amine with
an aldehyde or ketone and a reducing agent such as sodium
cyanoborohydride. Alternatively, alkylation may be achieved by
treating the amine with an alkylating agent such as an alkyl
halide, optionally in the presence of a base. Alternatively,
arylation may be achieved by treatment of the amine with an aryl
halide or sulfonate in the presence of a suitable catalyst/ligand
system, often a palladium (0) complex.
##STR00005##
[0100] 6) Alternatively, compounds of formula (IV), wherein R is
C.sub.1-C.sub.6alkoxy, may be made from a compound of formula
(VII), wherein R is C.sub.1-C.sub.6alkoxy and LG is a leaving
group, such as fluoro, chloro or sulfonate, via the displacement of
the leaving group by an amine of formula R.sup.1--NH.sub.2 or other
imine analogue followed by hydrolysis with a metal catalyst. See,
for example: Chemical Communications (2009), (14), 1891-1893 or
Journal of Organic Chemistry (2000), 65(8), 2612-2614.
##STR00006##
Compounds of formula (VII) and amines of formula R.sup.1--NH.sub.2
are either known compounds or may be made by methods known to a
person skilled in the art.
[0101] 7) Alternatively, compounds of formula (I), may be made by
the treatment of compounds of formula (IX) with a carboxylic acid
of formula Q.sup.1-COOH or an acid halide of formula Q.sup.1-COHal,
wherein Hal is Cl, F or Br, under standard conditions as described
in 1).
##STR00007##
[0102] 8) Compounds of formula (IX) may be formed from compounds of
formula (VIII), wherein P is a suitable protecting group and R is
OH, Cl or C.sub.1-C.sub.6alkoxy, by amide bond formation with an
amine of formula NHR.sup.2Q.sup.2 under standard conditions as
described in 1), followed by removal of the protecting group P
under standard conditions.
##STR00008##
[0103] 9) Compounds of formula (VIII), wherein R is OH or
C.sub.1-C.sub.6alkoxy, may be made by the protection of the amine
functionality in compounds of formula (IV), wherein R is OH or
C.sub.1-C.sub.6alkoxy. Suitable protecting groups include
carbamates (such as tert-butyloxycarbonyl, allyloxycarbonyl and
benzyloxycarbonyl), trialkylsilyl groups (such as
tert-butyldimethyl-silyl) and acyl groups (such as acetyl).
[0104] 10) For compounds of formula (VIII) and compounds of formula
(IV), the esters, wherein R is C.sub.1-C.sub.6alkoxy, may be
hydrolysed to the acids, wherein R is OH, by treatment with an
alkali hydroxide, such as sodium hydroxide, in a solvent, such as
ethanol. The acids may be converted to the acid chlorides, wherein
R is Cl, by treatment with thionyl chloride or oxalyl chloride as
described in 2) and 3).
[0105] 11) Alternatively, compounds of formula (IV), wherein R is
OH, Cl, F, Br or C.sub.1-C.sub.6alkoxy, may be converted directly
to compounds of formula (IX) by amide bond formation with an amine
of formula NHR.sup.2Q.sup.2 under standard conditions as described
in 1).
[0106] 12) Alternatively, compounds of formula (IX) may be made
from compounds of formula (XI), wherein LG is a leaving group such
as iodo, bromo, chloro or sulfonate, by displacement of the leaving
group with a compound of formula R.sup.1--NH.sub.2 or other imine
analogue followed by hydrolysis with a metal catalyst. See for
example: Chemical Communications (2009), (14), 1891-1893 or Journal
of Organic Chemistry (2000), 65(8), 2612-2614.
[0107] 13) Compounds of formula (XI) may be made from compounds of
formula (X), wherein R is Cl or OH and LG is a leaving group as
described in 12), via amide bond formation under standard
conditions as described in 1). Compounds of formula (X) and formula
(IV) are either known compounds or may be made by methods known to
the person skilled in the art.
##STR00009##
[0108] 14) An alternative synthesis of compounds of formula (IX),
wherein R.sup.1 is hydrogen, may be achieved by the reduction of
nitro compounds of formula (XIII), such as by treatment with tin
chloride under acidic conditions, or hydrogenation catalysed by a
noble metal such as palladium on carbon.
##STR00010##
[0109] 15) Compounds of formula (XIII) may be derived from
compounds of formula (XII), wherein R is OH, Cl, or
C.sub.1-C.sub.6alkoxy, via acylation with an amine of formula
NHR.sup.2Q.sup.2 under the standard conditions as described in
1).
[0110] 16) For compounds of formula (XII), the esters, wherein R is
C.sub.1-C.sub.6alkoxy, may be hydrolysed to the acids, wherein R is
OH, by treatment with an alkali hydroxide, such as sodium
hydroxide, in a solvent, such as ethanol as described in 3). The
acids may be converted to the acid chlorides, wherein R is Cl, by
treatment with thionyl chloride or oxalyl chloride as described in
2). Compounds of formula (XII) are either known or may be made by
methods known to a person skilled in the art.
[0111] 17) Compounds of formula (XII) can be made from a compound
of formula (XIV) wherein LG is halogen, such as fluorine or
chlorine, by reaction with methanol in the presence of a base, such
as NaH.
##STR00011##
The displacement of a halogen with an oxygen nucleophile can also
be carried out on intermediates of formula (XIII).
[0112] The compounds of formula (I) can be used to control
infestations of insect pests such as Lepidoptera, Diptera,
Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera,
Siphonaptera, Hymenoptera and Isoptera and also other invertebrate
pests, for example, acarine, nematode and mollusc pests. Insects,
acarines, nematodes and molluscs are hereinafter collectively
referred to as pests. The pests which may be controlled by the use
of the invention compounds include those pests associated with
agriculture (which term includes the growing of crops for food and
fiber products), horticulture and animal husbandry, companion
animals, forestry and the storage of products of vegetable origin
(such as fruit, grain and timber); those pests associated with the
damage of man-made structures and the transmission of diseases of
man and animals; and also nuisance pests (such as flies).
[0113] Examples of pest species which may be controlled by the
compounds of formula (I) include: Myzus persicae (aphid), Aphis
gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids),
Dysdercus spp. (capsids), Nilaparvata lugens (planthopper),
Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs),
Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs),
Frankliniella occidentalis (thrip), Thrips spp. (thrips),
Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus
grandis (boll weevil), Aonidiella spp. (scale insects),
Trialeurodes spp. (white flies), Bemisia tabaci (white fly),
Ostrinia nubilalis (European corn borer), Spodoptera littoralis
(cotton leafworm), Heliothis virescens (tobacco budworm),
Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton
bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae
(white butterfly), Plutella xylostella (diamond back moth), Agrotis
spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta
migratoria (locust), Chortiocetes terminifera (locust), Diabrotica
spp. (rootworms), Panonychus ulmi (European red mite), Panonychus
citri (citrus red mite), Tetranychus urticae (two-spotted spider
mite), Tetranychus cinnabarinus (carmine spider mite),
Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus
latus (broad mite), Brevipalpus spp. (flat mites), Boophilus
microplus (cattle tick), Dermacentor variabilis (American dog
tick), Ctenocephalides felis (cat flea), Liriomyza spp.
(leafminer), Musca domestica (housefly), Aedes aegypti (mosquito),
Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp.
(blowflies), Blattella germanica (cockroach), Periplaneta americana
(cockroach), Blatta orientalis (cockroach), termites of the
Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae
(for example Neotermes spp.), the Rhinotermitidae (for example
Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R.
virginicus, R. hesperus, and R. santonensis) and the Termitidae
(for example Globitermes sulfureus), Solenopsis geminata (fire
ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and
Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root
knot nematodes), Globodera spp. and Heterodera spp. (cyst
nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp.
(banana burrowing nematodes), Tylenchulus spp. (citrus nematodes),
Haemonchus contortus (barber pole worm), Caenorhabditis elegans
(vinegar eelworm), Trichostrongylus spp. (gastro intestinal
nematodes) and Deroceras reticulatum (slug).
[0114] The invention therefore provides a method of controlling
insects, acarines, nematodes or molluscs which comprises applying
an insecticidally, acaricidally, nematicidally or molluscicidally
effective amount of a compound of formula (I), or a composition
containing a compound of formula (I), to a pest, a locus of pest,
preferably a plant, or to a plant susceptible to attack by a pest.
The compounds of formula (I) are preferably used against insects or
acarines.
[0115] The term "plant" as used herein includes seedlings, bushes
and trees.
[0116] Crops are to be understood as also including those crops
which have been rendered tolerant to herbicides or classes of
herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by
conventional methods of breeding or by genetic engineering. An
example of a crop that has been rendered tolerant to
imidazolinones, e.g. imazamox, by conventional methods of breeding
is Clearfield.RTM. summer rape (canola). Examples of crops that
have been rendered tolerant to herbicides by genetic engineering
methods include e.g. glyphosate- and glufosinate-resistant maize
varieties commercially available under the trade names
RoundupReady.RTM. and LibertyLink.RTM..
[0117] Crops are also to be understood as being those which have
been rendered resistant to harmful insects by genetic engineering
methods, for example Bt maize (resistant to European corn borer),
Bt cotton (resistant to cotton boll weevil) and also Bt potatoes
(resistant to Colorado beetle). Examples of Bt maize are the Bt 176
maize hybrids of NK.RTM. (Syngenta Seeds). Examples of transgenic
plants comprising one or more genes that code for an insecticidal
resistance and express one or more toxins are KnockOut.RTM.
(maize), Yield Gard.RTM. (maize), NuCOTIN33B.RTM. (cotton),
Bollgard.RTM. (cotton), NewLeaf.RTM. (potatoes), NatureGard.RTM.
and Protexcta.RTM..
[0118] Plant crops or seed material thereof can be both resistant
to herbicides and, at the same time, resistant to insect feeding
("stacked" transgenic events). For example, seed can have the
ability to express an insecticidal Cry3 protein while at the same
time being tolerant to glyphosate.
[0119] Crops are also to be understood as being those which are
obtained by conventional methods of breeding or genetic engineering
and contain so-called output traits (e.g. improved storage
stability, higher nutritional value and improved flavor).
[0120] In order to apply a compound of formula (I) as an
insecticide, acaricide, nematicide or molluscicide to a pest, a
locus of pest, or to a plant susceptible to attack by a pest, a
compound of formula (I) is usually formulated into a composition
which includes, in addition to the compound of formula (I), a
suitable inert diluent or carrier and, optionally, a surface active
agent (SFA). SFAs are chemicals which are able to modify the
properties of an interface (for example, liquid/solid, liquid/air
or liquid/liquid interfaces) by lowering the interfacial tension
and thereby leading to changes in other properties (for example
dispersion, emulsification and wetting). It is preferred that all
compositions (both solid and liquid formulations) comprise, by
weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to
60%, of a compound of formula (I). The composition is generally
used for the control of pests such that a compound of formula (I)
is applied at a rate of from 0.1 g to 10 kg per hectare, preferably
from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per
hectare.
[0121] When used in a seed dressing, a compound of formula (I) is
used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g),
preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per
kilogram of seed.
[0122] In another aspect the present invention provides an
insecticidal, acaricidal, nematicidal or molluscicidal composition
comprising an insecticidally, acaricidally, nematicidally or
molluscicidally effective amount of a compound of formula (I) and a
suitable carrier or diluent therefor. The composition is preferably
an insecticidal or acaricidal composition.
[0123] The compositions can be chosen from a number of formulation
types, including dustable powders (DP), soluble powders (SP), water
soluble granules (SG), water dispersible granules (WG), wettable
powders (WP), granules (GR) (slow or fast release), soluble
concentrates (SL), oil miscible liquids (OL), ultra low volume
liquids (UL), emulsifiable concentrates (EC), dispersible
concentrates (DC), emulsions (both oil in water (EW) and water in
oil (EO)), micro-emulsions (ME), suspension concentrates (SC),
aerosols, fogging/smoke formulations, capsule suspensions (CS) and
seed treatment formulations. The formulation type chosen in any
instance will depend upon the particular purpose envisaged and the
physical, chemical and biological properties of the compound of
formula (I).
[0124] Dustable powders (DP) may be prepared by mixing a compound
of formula (I) with one or more solid diluents (for example natural
clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite,
kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium
and magnesium carbonates, sulfur, lime, flours, talc and other
organic and inorganic solid carriers) and mechanically grinding the
mixture to a fine powder.
[0125] Soluble powders (SP) may be prepared by mixing a compound of
formula (I) with one or more water-soluble inorganic salts (such as
sodium bicarbonate, sodium carbonate or magnesium sulfate) or one
or more water-soluble organic solids (such as a polysaccharide)
and, optionally, one or more wetting agents, one or more dispersing
agents or a mixture of said agents to improve water
dispersibility/solubility. The mixture is then ground to a fine
powder. Similar compositions may also be granulated to form water
soluble granules (SG).
[0126] Wettable powders (WP) may be prepared by mixing a compound
of formula (I) with one or more solid diluents or carriers, one or
more wetting agents and, preferably, one or more dispersing agents
and, optionally, one or more suspending agents to facilitate the
dispersion in liquids. The mixture is then ground to a fine powder.
Similar compositions may also be granulated to form water
dispersible granules (WG).
[0127] Granules (GR) may be formed either by granulating a mixture
of a compound of formula (I) and one or more powdered solid
diluents or carriers, or from pre-formed blank granules by
absorbing a compound of formula (I) (or a solution thereof, in a
suitable agent) in a porous granular material (such as pumice,
attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths
or ground corn cobs) or by adsorbing a compound of formula (I) (or
a solution thereof, in a suitable agent) on to a hard core material
(such as sands, silicates, mineral carbonates, sulfates or
phosphates) and drying if necessary. Agents which are commonly used
to aid absorption or adsorption include solvents (such as aliphatic
and aromatic petroleum solvents, alcohols, ethers, ketones and
esters) and sticking agents (such as polyvinyl acetates, polyvinyl
alcohols, dextrins, sugars and vegetable oils). One or more other
additives may also be included in granules (for example an
emulsifying agent, wetting agent or dispersing agent).
[0128] Dispersible Concentrates (DC) may be prepared by dissolving
a compound of formula (I) in water or an organic solvent, such as a
ketone, alcohol or glycol ether. These solutions may contain a
surface active agent (for example to improve water dilution or
prevent crystallization in a spray tank).
[0129] Emulsifiable concentrates (EC) or oil-in-water emulsions
(EW) may be prepared by dissolving a compound of formula (I) in an
organic solvent (optionally containing one or more wetting agents,
one or more emulsifying agents or a mixture of said agents).
Suitable organic solvents for use in ECs include aromatic
hydrocarbons (such as alkylbenzenes or alkylnaphthalenes,
exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200;
SOLVESSO is a Registered Trade Mark), ketones (such as
cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl
alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as
N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of
fatty acids (such as C.sub.8-C.sub.10 fatty acid dimethylamide) and
chlorinated hydrocarbons. An EC product may spontaneously emulsify
on addition to water, to produce an emulsion with sufficient
stability to allow spray application through appropriate equipment.
Preparation of an EW involves obtaining a compound of formula (I)
either as a liquid (if it is not a liquid at room temperature, it
may be melted at a reasonable temperature, typically below
70.degree. C.) or in solution (by dissolving it in an appropriate
solvent) and then emulsifying the resultant liquid or solution into
water containing one or more SFAs, under high shear, to produce an
emulsion. Suitable solvents for use in EWs include vegetable oils,
chlorinated hydrocarbons (such as chlorobenzenes), aromatic
solvents (such as alkylbenzenes or alkylnaphthalenes) and other
appropriate organic solvents which have a low solubility in
water.
[0130] Microemulsions (ME) may be prepared by mixing water with a
blend of one or more solvents with one or more SFAs, to produce
spontaneously a thermodynamically stable isotropic liquid
formulation. A compound of formula (I) is present initially in
either the water or the solvent/SFA blend. Suitable solvents for
use in MEs include those hereinbefore described for use in ECs or
in EWs. An ME may be either an oil-in-water or a water-in-oil
system (which system is present may be determined by conductivity
measurements) and may be suitable for mixing water-soluble and
oil-soluble pesticides in the same formulation. An ME is suitable
for dilution into water, either remaining as a microemulsion or
forming a conventional oil-in-water emulsion.
[0131] Suspension concentrates (SC) may comprise aqueous or
non-aqueous suspensions of finely divided insoluble solid particles
of a compound of formula (I). SCs may be prepared by ball or bead
milling the solid compound of formula (I) in a suitable medium,
optionally with one or more dispersing agents, to produce a fine
particle suspension of the compound. One or more wetting agents may
be included in the composition and a suspending agent may be
included to reduce the rate at which the particles settle.
Alternatively, a compound of formula (I) may be dry milled and
added to water, containing agents hereinbefore described, to
produce the desired end product.
[0132] Aerosol formulations comprise a compound of formula (I) and
a suitable propellant (for example n-butane). A compound of formula
(I) may also be dissolved or dispersed in a suitable medium (for
example water or a water miscible liquid, such as n-propanol) to
provide compositions for use in non-pressurized, hand-actuated
spray pumps.
[0133] A compound of formula (I) may be mixed in the dry state with
a pyrotechnic mixture to form a composition suitable for
generating, in an enclosed space, a smoke containing the
compound.
[0134] Capsule suspensions (CS) may be prepared in a manner similar
to the preparation of EW formulations but with an additional
polymerization stage such that an aqueous dispersion of oil
droplets is obtained, in which each oil droplet is encapsulated by
a polymeric shell and contains a compound of formula (I) and,
optionally, a carrier or diluent therefor. The polymeric shell may
be produced by either an interfacial polycondensation reaction or
by a coacervation procedure. The compositions may provide for
controlled release of the compound of formula (I) and they may be
used for seed treatment. A compound of formula (I) may also be
formulated in a biodegradable polymeric matrix to provide a slow,
controlled release of the compound.
[0135] A composition may include one or more additives to improve
the biological performance of the composition (for example by
improving wetting, retention or distribution on surfaces;
resistance to rain on treated surfaces; or uptake or mobility of a
compound of formula (I)). Such additives include surface active
agents, spray additives based on oils, for example certain mineral
oils or natural plant oils (such as soy bean and rape seed oil),
and blends of these with other bio-enhancing adjuvants (ingredients
which may aid or modify the action of a compound of formula
(I)).
[0136] A compound of formula (I) may also be formulated for use as
a seed treatment, for example as a powder composition, including a
powder for dry seed treatment (DS), a water soluble powder (SS) or
a water dispersible powder for slurry treatment (WS), or as a
liquid composition, including a flowable concentrate (FS), a
solution (LS) or a capsule suspension (CS). The preparations of DS,
SS, WS, FS and LS compositions are very similar to those of,
respectively, DP, SP, WP, SC and DC compositions described above.
Compositions for treating seed may include an agent for assisting
the adhesion of the composition to the seed (for example a mineral
oil or a film-forming barrier).
[0137] Wetting agents, dispersing agents and emulsifying agents may
be surface SFAs of the cationic, anionic, amphoteric or non-ionic
type.
[0138] Suitable SFAs of the cationic type include quaternary
ammonium compounds (for example cetyltrimethyl ammonium bromide),
imidazolines and amine salts.
[0139] Suitable anionic SFAs include alkali metals salts of fatty
acids, salts of aliphatic monoesters of sulfuric acid (for example
sodium lauryl sulfate), salts of sulfonated aromatic compounds (for
example sodium dodecylbenzenesulfonate, calcium
dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of
sodium di-isopropyl- and tri-isopropyl-naphthalene sulfonates),
ether sulfates, alcohol ether sulfates (for example sodium
laureth-3-sulfate), ether carboxylates (for example sodium
laureth-3-carboxylate), phosphate esters (products from the
reaction between one or more fatty alcohols and phosphoric acid
(predominately mono-esters) or phosphorus pentoxide (predominately
di-esters), for example the reaction between lauryl alcohol and
tetraphosphoric acid; additionally these products may be
ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates,
taurates and lignosulfonates.
[0140] Suitable SFAs of the amphoteric type include betaines,
propionates and glycinates.
[0141] Suitable SFAs of the non-ionic type include condensation
products of alkylene oxides, such as ethylene oxide, propylene
oxide, butylene oxide or mixtures thereof, with fatty alcohols
(such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such
as octylphenol, nonylphenol or octylcresol); partial esters derived
from long chain fatty acids or hexitol anhydrides; condensation
products of said partial esters with ethylene oxide; block polymers
(comprising ethylene oxide and propylene oxide); alkanolamides;
simple esters (for example fatty acid polyethylene glycol esters);
amine oxides (for example lauryl dimethyl amine oxide); and
lecithins.
[0142] Suitable suspending agents include hydrophilic colloids
(such as polysaccharides, polyvinylpyrrolidone or sodium
carboxymethylcellulose) and swelling clays (such as bentonite or
attapulgite).
[0143] A compound of formula (I) may be applied by any of the known
means of applying pesticidal compounds. For example, it may be
applied, formulated or unformulated, to the pests or to a locus of
the pests (such as a habitat of the pests, or a growing plant
liable to infestation by the pests) or to any part of the plant,
including the foliage, stems, branches or roots, to the seed before
it is planted or to other media in which plants are growing or are
to be planted (such as soil surrounding the roots, the soil
generally, paddy water or hydroponic culture systems), directly or
it may be sprayed on, dusted on, applied by dipping, applied as a
cream or paste formulation, applied as a vapor or applied through
distribution or incorporation of a composition (such as a granular
composition or a composition packed in a water-soluble bag) in soil
or an aqueous environment.
[0144] A compound of formula (I) may also be injected into plants
or sprayed onto vegetation using electrodynamic spraying techniques
or other low volume methods, or applied by land or aerial
irrigation systems.
[0145] Compositions for use as aqueous preparations (aqueous
solutions or dispersions) are generally supplied in the form of a
concentrate containing a high proportion of the active ingredient,
the concentrate being added to water before use. These
concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs,
WPs, WGs and CSs, are often required to withstand storage for
prolonged periods and, after such storage, to be capable of
addition to water to form aqueous preparations which remain
homogeneous for a sufficient time to enable them to be applied by
conventional spray equipment. Such aqueous preparations may contain
varying amounts of a compound of formula (I) (for example 0.0001 to
10%, by weight) depending upon the purpose for which they are to be
used.
[0146] A compound of formula (I) may be used in mixtures with
fertilizers (for example nitrogen-, potassium- or
phosphorus-containing fertilizers). Suitable formulation types
include granules of fertilizer. The mixtures preferably contain up
to 25% by weight of the compound of formula (I).
[0147] The invention therefore also provides a fertilizer
composition comprising a fertilizer and a compound of formula
(I).
[0148] The compositions of this invention may contain other
compounds having biological activity, for example micronutrients or
compounds having fungicidal activity or which possess plant growth
regulating, herbicidal, insecticidal, nematicidal or acaricidal
activity.
[0149] The compound of formula (I) may be the sole active
ingredient of the composition or it may be admixed with one or more
additional active ingredients such as a pesticide, fungicide,
synergist, herbicide or plant growth regulator where appropriate.
An additional active ingredient may: provide a composition having a
broader spectrum of activity or increased persistence at a locus;
synergize the activity or complement the activity (for example by
increasing the speed of effect or overcoming repellency) of the
compound of formula (I); or help to overcome or prevent the
development of resistance to individual components. The particular
additional active ingredient will depend upon the intended utility
of the composition. Examples of suitable pesticides include the
following:
a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,
esfenvalerate, deltamethrin, cyhalothrin (in particular
lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin,
tefluthrin, fish safe pyrethroids (for example ethofenprox),
natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin,
prallethrin or
5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidene-
methyl)cyclopropane carboxylate; b) Organophosphates, such as
profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl,
demeton-s-methyl, heptenophos, thiometon, fenamiphos,
monocrotophos, profenofos, triazophos, methamidophos, dimethoate,
phosphamidon, malathion, chlorpyrifos, phosalone, terbufos,
fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,
pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c)
Carbamates (including aryl carbamates), such as pirimicarb,
triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,
aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,
methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron,
triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e)
Organic tin compounds, such as cyhexatin, fenbutatin oxide or
azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate;
g) Macrolides, such as avermectins or milbemycins, for example
abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad,
azadirachtin or spinetoram; h) Hormones or pheromones; i)
Organochlorine compounds, such as endosulfan (in particular
alpha-endosulfan), benzene hexachloride, DDT, chlordane or
dieldrin; j) Amidines, such as chlordimeform or amitraz; k)
Fumigant agents, such as chloropicrin, dichloropropane, methyl
bromide or metam; l) Neonicotinoid compounds, such as imidacloprid,
thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam,
clothianidin, nithiazine or flonicamid; m) Diacylhydrazines, such
as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl
ethers, such as diofenolan or pyriproxifen;
o) Indoxacarb;
p) Chlorfenapyr;
q) Pymetrozine;
[0150] r) Spirotetramat, spirodiclofen or spiromesifen; s)
Diamides, such as flubendiamide, chlorantraniliprole or
cyantraniliprole;
t) Sulfoxaflor; or
u) Metaflumizone.
[0151] In addition to the major chemical classes of pesticide
listed above, other pesticides having particular targets may be
employed in the composition, if appropriate for the intended
utility of the composition. For instance, selective insecticides
for particular crops, for example stemborer specific insecticides
(such as cartap) or hopper specific insecticides (such as
buprofezin) for use in rice may be employed. Alternatively
insecticides or acaricides specific for particular insect
species/stages may also be included in the compositions (for
example acaricidal ovo-larvicides, such as clofentezine,
flubenzimine, hexythiazox or tetradifon; acaricidal motilicides,
such as dicofol or propargite; acaricides, such as bromopropylate
or chlorobenzilate; or growth regulators, such as hydramethylnon,
cyromazine, methoprene, chlorfluazuron or diflubenzuron).
[0152] Examples of fungicidal compounds which may be included in
the composition of the invention are
(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoaceta-
mide (SSF-129),
4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide-
,
.alpha.-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-.gamma.-butyrolacton-
e, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide
(IKF-916, cyamidazosulfamid),
3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide
(RH-7281, zoxamide),
N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide
(MON65500),
N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide
(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,
acibenzolar (CGA245704), alanycarb, aldimorph, anilazine,
azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol,
bitertanol, blasticidin S, bromuconazole, bupirimate, captafol,
captan, carbendazim, carbendazim chlorhydrate, carboxin,
carpropamid, carvone, CGA41396, CGA41397, chinomethionate,
chlorothalonil, chlorozolinate, clozylacon, copper containing
compounds such as copper oxychloride, copper oxyquinolate, copper
sulfate, copper tallate and Bordeaux mixture, cymoxanil,
cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulfide
1,1'-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb,
difenoconazole, difenzoquat, diflumetorim,
O,O-di-iso-propyl-5-benzyl thiophosphate, dimefluazole,
dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap,
dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine,
doguadine, edifenphos, epoxiconazole, ethirimol,
ethyl-(Z)--N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino-
]thio)-.beta.-alaninate, etridiazole, famoxadone, fenamidone
(RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid
(KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,
fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,
flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil,
flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine,
hexaconazole, hydroxyisoxazole, hymexazole, imazalil,
imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole,
iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl
carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,
LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim,
mepronil, metalaxyl, metconazole, metiram, metiram-zinc,
metominostrobin, myclobutanil, neoasozin, nickel
dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,
organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid,
oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron,
phenazin oxide, phosetyl-Al, phosphorus acids, phthalide,
picoxystrobin (ZA1963), polyoxin D, polyram, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
pyroxyfur, pyrrolnitrin, quaternary ammonium compounds,
quinomethionate, quinoxyfen, quintozene, sipconazole (F-155),
sodium pentachlorophenate, spiroxamine, streptomycin, sulfur,
tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,
thifluzamid, 2-(thiocyanomethylthio)benzothiazole,
thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl,
tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide,
tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine,
triflumizole, triticonazole, validamycin A, vapam, vinclozolin,
zineb and ziram.
[0153] The compounds of formula (I) may be mixed with soil, peat or
other rooting media for the protection of plants against
seed-borne, soil-borne or foliar fungal diseases.
[0154] Examples of suitable synergists for use in the compositions
include piperonyl butoxide, sesamex, safroxan and dodecyl
imidazole.
[0155] Suitable herbicides and plant-growth regulators for
inclusion in the compositions will depend upon the intended target
and the effect required.
[0156] An example of a rice selective herbicide which may be
included is propanil. An example of a plant growth regulator for
use in cotton is PIX.TM..
[0157] Some mixtures may comprise active ingredients which have
significantly different physical, chemical or biological properties
such that they do not easily lend themselves to the same
conventional formulation type. In these circumstances other
formulation types may be prepared. For example, where one active
ingredient is a water insoluble solid and the other a water
insoluble liquid, it may nevertheless be possible to disperse each
active ingredient in the same continuous aqueous phase by
dispersing the solid active ingredient as a suspension (using a
preparation analogous to that of an SC) but dispersing the liquid
active ingredient as an emulsion (using a preparation analogous to
that of an EW). The resultant composition is a suspoemulsion (SE)
formulation.
EXAMPLES
[0158] The following abbreviations were used throughout this
section: s=singlet; bs=broad singlet; d=doublet; dd=double doublet;
dt=double triplet; t=triplet, tt=triple triplet, q=quartet,
sept=septet; m=multiplet; Me=methyl; Et=ethyl; Pr=propyl; Bu=butyl;
M.p.=melting point; RT=retention time, MH.sup.+=molecular cation
(i.e. measured molecular weight).
Example I1
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoro-methylpropyl)phe-
nyl]-2-fluoro-3-nitrobenzamide
##STR00012##
[0160] To a solution of
2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)pheny-
lamine (Example I6) (20 g, 47.1 mmol) and 2-fluoro-3-nitrobenzoic
acid (17.4 g, 94.2 mmol) in dichloromethane (230 ml) was added
triethylamine (19.7 ml, 141 mmol) and
bis(2-oxo-3-oxazolidinyl)phosphonic chloride ("BOP-Cl") (23.98 g,
94 mmol). The reaction mixture was heated to reflux for 6 hours.
The reaction mixture was cooled to ambient temperature and quenched
by the addition of aqueous hydrochloric acid (1N). The mixture was
then extracted three times with dichloromethane. The combined
organic extracts were washed with saturated aqueous sodium hydrogen
carbonate, dried over sodium sulfate and concentrated. The residue
was purified by column chromatography on silica gel (eluent:
cyclohexane/ethyl acetate 7:3) to give
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phe-
nyl]-2-fluoro-3-nitrobenzamide (12 g, 43% yield). .sup.1H NMR
(CDCl.sub.3, 400 MHz): 8.48 (t, 1H), 8.30 (t, 1H), 8.18 (db, 1H),
7.86 (s, 1H), 7.75 (s, 1H), 7.54 (t, 1H) ppm.
[0161] The following compound was made by the same procedure:
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]--
2-fluoro-3-nitro-benzamide
[0162] .sup.1H NMR (CDCl.sub.3, 400 MHz): 8.48 (t, 1H), 8.28 (t,
1H), 8.14 (db, 1H), 7.68 (s, 2H), 7.54 (t, 1H) ppm.
Example I2
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-phe-
nyl]-2-fluoro-3-nitrobenzamide
##STR00013##
[0164] To a suspension of 2-fluoro-3-nitrobenzoic acid (6.3 g, 34
mmol) in dichloromethane (20 ml) was added oxalyl chloride (4.3 ml)
at ambient temperature, followed by N,N-dimethylformamide (0.2 ml).
The reaction mixture was stirred for 1 hour at ambient temperature
and then heated to reflux for 3 hours. The reaction mixture was
allowed to cool to ambient temperature and then concentrated. The
residue was suspended in tetrahydrofuran (50 ml).
2-Ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylanilin-
e (preparation as described in WO 08/074,427) (10 g, 28.3 mmol) was
dissolved in tetrahydro-furan (50 ml) and pyridine (6.8 ml, 84.9
mmol) was added. The reaction mixture was stirred at ambient
temperature for 3 hours, then at reflux for 3 hours. The reaction
was quenched by addition of saturated aqueous sodium hydrogen
carbonate (100 ml) and the mixture extracted twice with ethyl
acetate (2.times. 200 ml). The combined organic extracts were dried
over sodium sulfate and concentrated. The residue was purified by
column chromatography on silica gel (eluent: cyclohexane/ethyl
acetate 4:1 to 0:1) to give
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-fluoro-3-nitrobenzamide (6.32 g, 43% yield).
[0165] .sup.1H NMR (CDCl.sub.3, 400 MHz): 8.34 (m, 1H), 8.22 (m,
1H), 8.02 (bs, 1H), 7.45 (t, 1H), 7.48 (s, 2H), 2.70 (q, 2H), 1.22
(t, 3H).
Example I3
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-phe-
nyl]-2-bromo-3-nitrobenzamide
##STR00014##
[0167] To a suspension of 2-bromo-3-nitrobenzoic acid (2.870 g,
0.0117 mol) in toluene (29 ml) was added N,N-dimethylformamide (90
.mu.l) at ambient temperature, followed by slow addition of thionyl
chloride (1.69 ml, 0.02332 mol). The reaction mixture was stirred
for 1 hour at 100.degree. C. The reaction mixture was allowed to
cool to ambient temperature and the toluene was evaporated. The
appropriate amount of acyl chloride was dissolved in THF and use
without extra purification.
[0168] To a solution of
2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylanilin-
e (preparation as described in WO 08/074,427) (106 mg, 0.3 mmol) in
tetrahydrofuran (0.5 ml) was added pyridine (72.6 .mu.l, 0.9 mmol)
at 0 to 5.degree. C. A solution of 2-bromo-3-nitrobenzoic acid
chloride (87 mg, 0.33 mmol) in tetrahydrofuran (0.5 ml) was added.
The reaction mixture was stirred at ambient temperature for 3
hours, then at reflux for 15 hours. After 15 hours, the reaction
was not complete so N,N-dimethylacetamide ("DMA") (0.1 equivalents)
and more 2-bromo-3-nitrobenzoic acid chloride (0.2 equivalents)
were added. The reaction mixture was stirred at ambient temperature
for 41 hours. After 41 hours, the reaction was quenched by addition
of saturated aqueous sodium hydrogen carbonate (10 ml) and the
mixture extracted twice with ethyl acetate (2.times.20 ml). The
combined organic extracts were dried over sodium sulfate and
concentrated. The residue was purified by column chromatography on
silica gel (eluent: cyclohexane/ethyl acetate 6:1) to give
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-meth-
ylphenyl]-2-bromo-3-nitrobenzamide (0.133 g, 76% yield).
[0169] .sup.1H NMR (CDCl.sub.3, 400 MHz): 7.78 (dd, 1H), 7.72 (dd,
1H), 7.53 (t, 1H), 7.32 (s, 2H), 7.17 (bs, 1H), 2.71 (q, 2H), 2.40
(s, 3H), 1.19 (t, 3H).
Example I4
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-phe-
nyl]-2-methoxy-3-nitrobenzamide
##STR00015##
[0171] To a suspension of
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-fluoro-3-nitrobenzamide (Example I2) (5 g, 9.6 mmol) in
methanol (195 ml) was added potassium carbonate (2.6 g, 16.2 mmol)
at ambient temperature. The reaction mixture was stirred for 16
hours at ambient temperature. The reaction mixture was concentrated
and the residue was dissolved in dichloromethane. The organic phase
was washed with water, dried over sodium sulfate and concentrated.
The residue was purified by column chromatography on silica gel
(eluent: cyclohexane/ethyl acetate 3:1) to give
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-methoxy-3-nitrobenzamide (5.1 g, 99% yield). .sup.1H NMR
(400 MHz, CDCl.sub.3): 8.90 (bs, 1H), 8.32 (d, 1H), 7.97 (d, 1H),
7.38 (m, 3H), 4.19 (s, 3H), 2.70 (q, 2H), 2.24 (s, 3H), 1.20 (t,
3H) ppm.
[0172] The following compounds were made by the same procedure:
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phen-
yl]-2-methoxy-3-nitrobenzamide
[0173] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.23 (bs, 1H), 8.45 (dd,
1H), 8.07 (dd, 1H), 7.84 (s, 1H), 7.71 (s, 1H), 7.46 (t, 1H), 4.18
(s, 3H) ppm.
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]--
2-methoxy-3-nitrobenzamide
[0174] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.22 (bs, 1H), 8.42 (d,
1H), 8.07 (d, 1H), 7.68 (s, 2H), 7.44 (t, 1H), 4.15 (s, 3H)
ppm.
[0175] A similar procedure was applied to
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-bromo-3-nitrobenzamide (Example I3) to give
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-methoxy-3-nitrobenzamide (92% yield).
Example I5
3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-me-
thylphenyl]-2-methoxybenzamide
##STR00016##
[0177] To a solution of
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphe-
nyl]-2-methoxy-3-nitrobenzamide (Example I4) (5.1 g, 9.57 mmol) in
isopropanol (50 ml) was added tin chloride (6.5 g, 34.5 mmol) at
ambient temperature. The mixture was cooled to 0.degree. C. and
concentrated aqueous hydrochloric acid (10 ml) was added slowly.
The reaction mixture was stirred at 80.degree. C. for 0.5 hours.
One third of the total volume of isopropanol was evaporated. Water
(100 ml) was added to the concentrated mixture and aqueous sodium
hydroxide (4N) was added to adjust the pH to 7 to 8. The aqueous
phase was extracted three times with ethyl acetate (3.times.200
ml). The combined organic extracts were dried over sodium sulfate
and concentrated. The residue was purified by column chromatography
on silica gel (eluent: cyclohexane/ethyl acetate 2:1 to 1:1) to
give
3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-m-
ethylphenyl]-2-methoxy benzamide (2.3 g, 48% yield).
[0178] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.12 (bs, 1H), 7.37 (dd,
1H), 7.26 (s, 2H), 6.91 (t, 1H), 6.80 (dd, 1H), 3.90 (bs, 2H), 3.80
(s, 3H), 2.60 (q, 2H), 2.24 (s, 3H), 1.11 (t, 3H) ppm.
[0179] The following compounds were made by the same procedure:
3-Amino-N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpro-
pyl)-phenyl]-2-methoxybenzamide
[0180] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.73 (bs, 1H), 7.61 (s,
1H), 7.47 (dd, 1H), 6.98 (t, 1H), 6.88 (dd, 1H), 3.91 (s, 3H), 3.85
(bs, 2H) ppm.
3-Amino-N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-
-phenyl]-2-methoxybenzamide
[0181] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.65 (s, 2H), 7.54 (d,
1H), 7.10 (t, 1H), 6.98 (d, 1H), 3.98 (s, 3H), 3.93 (bs, 2H)
ppm.
Example I6
2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-phenyl-
amine
##STR00017##
[0183] 4-(1,2,2,3,3,3-Hexafluoro-1-trifluoromethylethyl)phenylamine
(prepared according to EP 1,006,102) (175.8 g, 565 mmol) was
dissolved in acetonitrile (1000 ml) and N-chloro-succinimide
("NCS") (76.2 g, 570.7 mmol) was added. The reaction mixture was
heated to reflux for 90 minutes. The reaction mixture was
concentrated under vacuum, the residue suspended in diethyl ether
and the solids removed via filtration. The filtrate was
concentrated and the residue was purified by column chromatography
on silica gel (eluent: cyclohexane/dichloromethane 9:1) to give
2-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenylami-
ne. The same procedure was repeated using N-bromosuccinimide
("NBS") (100.5 g, 565 mmol) as reagent. This time the residue was
purified by column chromatography on silica gel (eluent:
cyclohexane/dichloromethane 2:1) to give
2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl-
amine (143.3 g, 59.7% yield).
[0184] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.70 (s, 1H), 7.42 (s,
1H), 4.82 (s, 2H) ppm.
Example I7
4-cyano-2-methylbenzoic acid methyl ester
##STR00018##
[0186] To a solution of 4-bromo-2-methylbenzoic acid (108 g, 471
mmol) in N,N-dimethylformamide (4 L) under a nitrogen atmosphere
was added zinc (II) cyanide (88.5 g, 753.6 mmol) and
tetrakis(triphenylphosphine)palladium (65 g, 56.60 mmol). The
reaction mixture was stirred at 100.degree. C. for 16 hours. The
reaction mixture was diluted with toluene and the phases were
separated. The aqueous phase was extracted twice with toluene. The
combined organic phases were washed with brine and saturated
aqueous ammonium hydroxide, dried over sodium sulfate and
concentrated. The residue was purified by column chromatography on
silica gel (eluent: ethyl acetate/cyclohexane 1:5) to give
4-cyano-2-methylbenzoic acid methyl ester (73 g, 89% yield).
.sup.1H NMR (400 MHz, CDCl.sub.3): 7.78 (d, 1H), 7.52 (m, 2H), 3.92
(s, 3H), 2.62 (s, 3H) ppm.
Example I8
4-cyano-2-methylbenzoic acid
##STR00019##
[0188] To a solution of 4-cyano-2-methylbenzoic acid (Example I7)
(61 g, 348 mmol) in a mixture of water (0.360 ml) and
tetrahydrofuran (1.4 l) was added lithium hydroxide hydrate (31.4
g, 748.2 mmol). The reaction mixture was stirred at ambient
temperature for 3 hours. The reaction mixture was concentrated. The
residue was acidified by addition of aqueous hydrochloric acid (1N)
and extracted with a mixture of methanol and chloroform (5:95). The
organic phase was dried over sodium sulfate and concentrated. The
residue was crystallized in a mixture of ethyl acetate and
cyclohexane to give 4-cyano-2-methylbenzoic acid (55.5 g, 99%
yield). .sup.1H NMR (400 MHz, CDCl.sub.3): 7.89 (d, 1H), 7.80 (s,
1H), 7.72 (d, 1H), 2.51 (s, 3H) ppm.
Example P1
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-phe-
nyl]-3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound
No. A5 of Table A)
##STR00020##
[0190] To a solution of 4-cyano-2-methylbenzoic acid (Example I8)
(0.141 g, 0.8 mmol) and N,N-dimethylformamide (2 drops) in
dichloromethane (5 ml) under a nitrogen atmosphere was added oxalyl
chloride (0.074 ml, 0.88 mmol). The reaction mixture was stirred
for one hour at ambient temperature and then at 60.degree. C. for
1.5 hours. The reaction mixture was concentrated and the residue
dissolved in tetrahydrofuran (10 ml). The solution was added
dropwise to a solution of
3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-6--
methylphenyl]-2-methoxybenzamide (Example I5) (0.37 g, 0.73 mmol)
and pyridine (0.12 ml, 1.46 mmol) in tetrahydrofuran (10 ml). The
reaction mixture was stirred at ambient temperature for 16 hours.
The reaction mixture was poured into aqueous sodium hydrogen
carbonate (1M) and the mixture extracted three times with ethyl
acetate. The combined organic phases were dried over sodium sulfate
and concentrated. The residue was purified by column chromatography
on silica gel (eluent: ethyl acetate/cyclohexane 1:3) to give
Compound No. A5 of Table A (0.240 g, 51% yield). M.p.
104-105.degree. C. .sup.1H NMR (400 MHz, CDCl.sub.3): 8.68 (d, 1H),
8.62 (s, 1H), 8.01 (s, 1H), 7.92 (d, 1H), 7.66 (m, 3H), 7.41 (m,
3H), 4.00 (s, 3H), 2.72 (q, 2H), 2.62 (s, 3H), 2.39 (s, 3H), 1.25
(t, 3H) ppm.
[0191] The following compounds were made by the same procedure:
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphen-
yl]-3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound
No. A3 of Table A)
[0192] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.76 (m, 2H), 8.71 (d,
1H), 7.98 (m, 1H), 7.71 (dd, 1H), 7.39 (m, 3H), 7.27 (dd, 1H), 7.18
(m, 1H), 4.03 (s, 3H), 2.73 (q, 2H), 2.39 (s, 3H), 1.25 (t, 3H)
ppm.
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phen-
yl]-3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound
No. B2 of Table B)
[0193] M.p. 178-179.degree. C. .sup.1H NMR (400 MHz, CDCl.sub.3):
9.12 (bs, 1H), 8.79 (bs, 1H), 8.73 (d, 1H), 7.79-7.72 (m, 2H), 7.84
(s, 1H), 7.72 (s, 1H), 7.38 (t, 1H), 7.25 (m, 1H), 7.17 (m, 1H),
4.07 (s, 3H) ppm.
N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-phe-
nyl]-3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound
No. B1 of Table B)
[0194] M.p. 109-110.degree. C. .sup.1H NMR (400 MHz, CDCl.sub.3):
9.04 (bs, 1H), 8.69 (d, 1H), 8.10 (s, 1H), 7.93 (dd, 1H), 7.84 (s,
1H), 7.72 (s, 1H), 7.63 (m, 3H), 7.40 (t, 1H), 4.04 (s, 3H), 2.61
(s, 3H) ppm.
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]--
3-(4-fluoro-2-chlorobenzoylamino)-2-methoxybenzamide (Compound No.
C1 of Table C)
[0195] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.12 (bs, 1H), 8.79-8.72
(m, 2H), 7.97 (m, 1H), 7.91 (dd, 1H), 7.68 (s, 2H), 7.48 (t, 1H),
7.25 (m, 1H), 7.16 (m, 1H), 4.04 (s, 3H) ppm.
N-[2,6-dichloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)phenyl]--
3-(4-cyano-2-methylbenzoylamino)-2-methoxybenzamide (Compound No.
C2 of Table C)
[0196] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.99 (bs, 1H), 8.70 (d,
1H), 8.02 (s, 1H), 7.92 (dd, 1H), 7.68 (s, 2H), 7.62 (s, 3H), 7.40
(t, 1H), 4.02 (s, 3H), 2.60 (s, 3H) ppm.
[0197] The following compound was made by the same procedure except
that the acyl chloride was used directly and triethylamine was used
instead of pyridine:
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphen-
yl]-3-(4-fluorobenzoylamino)-2-methoxybenzamide (Compound No. A1 of
Table A)
[0198] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.68 (s, 1H), 8.57 (d,
1H), 8.30 (s, 1H), 7.89 (m, 2H), 7.80 (dd, 1H), 7.30 (m, 3H), 7.17
(m, 2H), 3.94 (s, 3H), 2.66 (q, 2H), 2.32 (s, 3H), 1.15 (t,
3H).
Example P2
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methyl-phe-
nyl]-3-(4-cyanobenzoylamino)-2-methoxybenzamide (Compound No. A4 of
Table A)
##STR00021##
[0200] To a solution of
3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-6--
methylphenyl]-2-methoxybenzamide (Example I5) (30 mg, 0.06 mmol) in
tetrahydrofuran (1.2 ml) was added triethylamine (25 .mu.l, 0.18
mmol). 4-Cyanobenzoic acid (17.6 mg, 0.12 mmol) and
bis(2-oxo-3-oxazolidinyl)phosphonic chloride ("BOP-Cl") (30.4 mg,
0.12 mmol) were added. The reaction mixture was heated to reflux
for 6 hours. The reaction mixture was cooled to ambient temperature
and concentrated. The residue was dissolved in dichloromethane and
washed with aqueous hydrochloric acid (1N) and with aqueous sodium
hydrogen carbonate (saturated). The organic extract was dried over
sodium sulfate and concentrated. The residue was purified by column
chromatography on silica gel (eluent: cyclohexane/ethyl acetate
5:3) to give Compound No. A4 of Table A (35 mg, 93% yield). .sup.1H
NMR (400 MHz, CDCl.sub.3): 8.56 (m, 2H), 8.48 (bs, 1H), 7.97 (m,
2H), 7.82 (d, 1H), 7.78 (d, 2H), 7.30 (m, 3H), 3.94 (s, 3H), 2.65
(q, 2H), 2.30 (s, 3H), 1.13 (t, 3H) ppm.
[0201] The following compound was made by the same procedure:
N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphen-
yl]-3-(2-methyl-3-nitrobenzoylamino)-2-methoxybenzamide (Compound
No. A2 of Table A)
[0202] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.62 (d, 1H), 8.53 (s,
1H), 7.91 (m, 2H), 7.86 (d, 1H), 7.67 (d, 1H), 7.42 (t, 1H), 7.30
(m, 3H), 3.91 (s, 3H), 2.64 (q, 2H), 2.59 (s, 3H), 2.31 (s, 3H),
1.14 (t, 3H) ppm.
Example P3
N-{3-[2-Bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)--
phenylcarbamoyl]-2-methoxyphenyl}-2,4,6-trifluorobenzamide
##STR00022##
[0204] To a solution of 2,4,6-trifluorobenzoic acid (8.114 g, 46.08
mmol) and N,N-dimethylformamide (few drops) in dichloromethane (50
ml) under a nitrogen atmosphere was added oxalyl chloride (4.55 mL,
53.76 mmol). The reaction mixture was stirred for one hour at
ambient temperature and then at 60.degree. C. for 1.5 hours. The
reaction mixture was concentrated and the residue dissolved in
tetrahydrofuran (200 ml). The solution was added drop-wise to a
solution of
3-amino-N-[2-bromo-6-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpr-
opyl)phenyl]-2-methoxybenzamide (Example I5) (22.03 g, 38.40 mmol)
and pyridine (6.18 ml, 76.80 mmol) in tetrahydrofuran (200 ml). The
reaction mixture was stirred at ambient temperature for 2 hours.
The reaction mixture was poured into aqueous sodium hydrogen
carbonate (1M) and the mixture extracted three times with ethyl
acetate. The combined organic phases were dried over sodium sulfate
and concentrated. The residue was purified by filtration on silica
gel to give Compound No. B189 of Table B (28.0 g, 99% yield). M.p.
179.degree. C. .sup.1H NMR (400 MHz, CDCl.sub.3): 9.14 (s, 1H),
8.72 (d, 1H), 8.28 (s, 1H), 7.97 (q, 1H), 7.85 (s, 1H), 7.74 (s,
1H), 7.41 (t, 1H), 6.88 (t, 1H), 4.08 (s, 3H) ppm.
Example P4
Preparation of Benzamides from Acid Chlorides which is Amenable to
Parallel Synthesis
##STR00023##
[0206] Solution A was prepared by dissolving the amino derivative
(0.78 mmol), for example
3-amino-N-[2-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6--
bromophenyl]-2-methoxybenzamide (Example I5) in the case of
Compound No. B3 of Table B, in toluene (15.6 ml). Solution B was
prepared by dissolving the acid chloride (45 .mu.mol), for example
2-fluorobenzoyl chloride in the case of Compound No. B3 of Table B,
in toluene (0.36 ml). Solution A (0.6 ml, 30 .mu.mmol) was put in a
well and Solution B (0.36 ml, 45 .mu.mmol) and
diisopropylethylamine ("Hunig's Base") (30 .mu.l, 150 .mu.mol) were
added successively to the well. The reaction mixture was stirred at
80.degree. C. for 16 hours. The solvent was evaporated and the
mixture was diluted with a mixture of acetonitrile (0.6 ml) and
N,N-dimethylacetamide (0.2 ml) and then purified by HPLC to give
the desired compound.
[0207] This method was used to prepare a number of compounds in
parallel.
Example P5
Preparation of Benzamides from Carboxylic Acids which is Amenable
to Parallel Synthesis
##STR00024##
[0209] Solution A was prepared by dissolving the amino derivative
(0.65 mmol), for example
3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-m-
ethylphenyl]-2-methoxybenzamide (Example I5) in the case of
Compound No. A9 of Table A, in N,N-dimethylacetamide ("DMA") (9.6
ml). Solution B was prepared by dissolving the carboxylic acid
(37.5 .mu.mol), for example 2-chlorobenzoic acid in the case of
Compound No. A9 of Table A, in N,N-dimethylacetamide ("DMA") (0.38
ml). Solution C was prepared by dissolving
bis(2-oxo-3-oxazolidinyl)phosphinic chloride ("BOP-Cl") (1.95 mmol)
in N,N-dimethylacetamide ("DMA") (7.8 ml). Solution A (0.4 ml,
0.025 mmol) was put in a well and Solution B (0.38 ml, 37.5
.mu.mol), Solution C (0.2 mL, 50 .mu.mol) and diisopropylethylamine
("Hunig's Base") (40 .mu.l, 200 .mu.mol) were added successively to
the well. The reaction mixture was stirred at 100.degree. C. for 16
hours. The solvent was evaporated and the mixture was diluted with
a mixture of acetonitrile (0.6 ml) and N,N-dimethylacetamide (0.2
ml) and then purified by HPLC to give the desired compound.
[0210] This method was used to prepare a number of compounds in
parallel.
[0211] The following HPLC-MS method was used for the analysis of
the compounds of Table A to L:
[0212] Method 1:
TABLE-US-00001 MS ZQ Mass Spectrometer from Waters (single
quadrupole mass spectrometer), ionization method: electrospray,
polarity: positive ionization, capillary (kV) 3.00, cone (V) 30.00,
extractor (V) 3.00, source temperature (.degree. C.) 100,
desolvation temperature (.degree. C.) 200, cone gas flow (L/Hr)
200, desolvation gas flow (L/Hr) 250, mass range: 150 to 800 Da. LC
1100er Series HPLC from Agilent: quaternary pump, heated column
compartment and diode-array detector. Column: Waters Atlantis dc18;
length: 20 mm; internal diameter: 3 mm; particle size: 3 .mu.m,
temperature (.degree. C.) 40, DAD wavelength range (nm): 200 to
500, solvent gradient: A = 0.1% of formic acid in water and B: 0.1%
of formic acid in acetonitrile. Time (min) A % B % Flow (ml/min)
0.0 80 20 1.7 2.5 0.0 100 1.7 2.8 0.0 100 1.7 2.9 80 20 1.7
[0213] Method 2:
TABLE-US-00002 MS ZQ Mass Spectrometer from Waters (single
quadrupole mass spectrometer), ionization method: electrospray,
polarity: positive ionization, capillary (kV) 3.00, cone (V) 30.00,
extractor (V) 3.00, source temperature (.degree. C.) 100,
desolvation temperature (.degree. C.) 200, cone gas flow (L/Hr)
200, desolvation gas flow (L/Hr) 250, mass range: 150 to 800 Da. LC
1100er Series HPLC from Agilent: quaternary pump, heated column
compartment and diode-array detector. Column: Waters Atlantis dc18;
length: 20 mm; internal diameter: 3 mm; particle size: 3 .mu.m,
temperature (.degree. C.) 40, DAD wavelength range (nm): 200 to
500, solvent gradient: A = 0.1% of formic acid in water and B: 0.1%
of formic acid in acetonitrile. Time (min) A % B % Flow (ml/min)
0.0 90 10 1.7 5.5 0.0 100 1.7 5.8 0.0 100 1.7 5.9 90 10 1.7
[0214] Method 3:
TABLE-US-00003 MS ZQ Mass Spectrometer from Waters (Single
quadrupole mass spectrometer) Instrument Parameter: Ionisation
method: Electrospray Polarity: negative ions Capillary (kV) 3.00,
Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (.degree.
C.) 100, Desolvation Temperature (.degree. C.) 250, Cone Gas Flow
(L/Hr) 50, Desolvation Gas Flow (L/Hr) 400, Mass range: 150 to 1000
Da. LC HP 1100 HPLC from Agilent: solvent degasser, quaternary pump
(ZCQ)/ binary pump (ZDQ), heated column compartment and diode-array
detector. Column: Phenomenex Gemini C18, 3 .mu.m particle size, 110
Angstrom, 30 .times. 3 mm, Temp: 60.degree. C. DAD Wavelength range
(nm): 200 to 500 Solvent Gradient:. A = water + 0.05% HCOOH. B =
Acetonitril/Methanol (4:1, v:v) + 0.04% HCOOH Time (min) A % B %
Flow (ml/min) 0.00 95.0 5.0 1.7 2.00 0.00 100.00 1.7 2.80 0.00
100.00 1.7 2.90 95.0 5.0 1.7 3.00 95.0 5.0 1.7
[0215] Method 4:
TABLE-US-00004 MS ZQ Mass Spectrometer from Waters (Single
quadrupole mass spectrometer) Instrument Parameter: Ionisation
method: Electrospray. Polarity: negative ions Capillary (kV) 3.00,
Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (.degree.
C.) 100, Desolvation Temperature (.degree. C.) 250, Cone Gas Flow
(L/Hr) 50, Desolvation Gas Flow (L/Hr) 400. Mass range: 100 to 900
Da LC HP 1100 HPLC from Agilent: solvent degasser, quaternary pump
(ZCQ)/ binary pump (ZDQ), heated column compartment and diode-array
detector. Column: Phenomenex Gemini C18, 3 .mu.m particle size, 110
Angstrom, 30 .times. 3 mm, Temp: 60.degree. C. DAD Wavelength range
(nm): 200 to 500. Solvent Gradient: A = water + 0.05% HCOOH, B =
Acetonitril/Methanol (4:1, v:v) + 0.04% HCOOH Time (min) A % B %
Flow (ml/min) 0.00 95.0 5.0 1.7 2.00 0.00 100.00 1.7 2.80 0.00
100.00 1.7 2.90 95.0 5.0 1.7 3.00 95.0 5.0 1.7
TABLE-US-00005 TABLE A (Ia) ##STR00025## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method A1 4-fluorophenyl 3.87
624.8 2 A2 2-methyl-3-nitrophenyl -- -- A3 2-chloro-4-fluorophenyl
-- -- A4 4-cyanophenyl 3.77 631.9 2 A5 4-cyano-2-methylphenyl -- --
104 A6 2-chloropyrid-3-yl 3.65 641.8 2 A7 2-fluoropyrid-3-yl 3.79
625.8 2 A8 3-chlorophenyl 4.04 640.8 2 A9 2-chlorophenyl 3.94 640.8
2 A10 2-chloropyrid-4-yl 3.76 641.8 2 A11 5-bromopyrid-3-yl 3.75
687.7 2 A12 5-bromofuran-2-yl 3.98 676.7 2 A13 2-bromophenyl 3.94
686.7 2 A14 3-chloro-5- 4.3 709.8 2 trifluoromethylpyrid-2-yl A15
2-fluoro-3- 4.24 692.8 2 trifluoromethylphenyl A16
2,5-dichlorophenyl 4.13 674.8 2 A17 6-chloropyrid-3-yl 3.67 641.8 2
A18 4-nitrophenyl 3.86 651.8 2 A19 phenyl 3.84 606.8 2 A20
2,3-difluorophenyl 4.07 642.8 2 A21 5-chlorothiophen-2-yl 4.07
646.8 2 A22 2-methyl-4-nitrophenyl 175
TABLE-US-00006 TABLE B (Ib) ##STR00026## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method B1
4-cyano-2-methylphenyl -- -- B2 2-chloro-4-fluorophenyl 2.2 730.7 1
B3 2-fluorophenyl 2.23 696.6 1 B4 2-methylphenyl 2.17 692.7 1 B5
2-chlorophenyl 2.18 712.7 1 B6 4-cyanophenyl 2.07 703.7 1 B7
4-nitrophenyl 2.06 722.0 1 B8 4-methylphenyl 2.21 692.7 1 B9
4-fluoro-2-methylphenyl 2.18 710.7 1 B10 5-chloro-2-fluorophenyl
2.34 730.6 1 B11 2-chloro-4-nitrophenyl 2.19 757.7 1 B12 furan-2-yl
2.06 668.7 1 B13 4-trifluoromethoxyphenyl 2.29 762.7 1 B14
4-fluoro-3-trifluoro-methylphenyl 2.27 764.7 1 B15
4-trifluoromethylphenyl 2.05 746.7 1 B16 2-trifluoromethoxyphenyl
2.26 762.7 1 B17 2-methoxyphenyl 2.28 708.7 1 B18 phenyl 2.12 678.6
1 B19 4-fluorophenyl 2.13 696.7 1 B20 2-trifluoromethylphenyl 2.17
746.7 1 B21 4-methyl-1,2,3-thiadiazol-5-yl 2.05 700.6 1 B22
2,3-difluorophenyl 2.25 714.7 1 B23 2,4-difluorophenyl 2.26 714.7 1
B24 2-fluoro-5-trifluoromethylphenyl 2.34 764.7 1 B25
4-isopropylphenyl 4.55 719.07 2 B26 4-methylsulfanylphenyl 4.27
722.99 2 B27 2,5-dichlorophenyl 4.44 744.97 2 B28 4-methoxyphenyl
4.1 707 2 B29 2,4,5-trifluoro-3-chlorophenyl 4.59 764.98 2 B30
4-(pyrrol-1-yl)phenyl 4.35 742.06 2 B31
4-(1,2,3-thiadiazol-4-yl)phenyl 4.18 761.02 2 B32
(3,4-dihydro-2H-benzo[b][1,4]dioxepine)-7-yl 4.16 749.06 2 B33
4-biphenyl 4.54 753.08 2 B34 3-methylpyridin-2-yl 4.55 692 2 B35
2-fluoro-3-trifluoromethylphenyl 4.49 763 2 B36 2-bromophenyl 4.18
754.94 2 B37 pyridin-3-yl 3.57 677.98 2 B38 4-methoxythiophen-3-yl
4.41 712.99 2 B39 1,2,3-thiadiazol-4-yl 4.07 684.96 2 B41
5-phenyloxazol-4-yl 4.76 744.05 2 B42 2,5-dimethyl-2H-pyrazol-3-yl
3.91 695.04 2 B43 4-methyl-2-phenylpyrimidin-5-yl 4.41 769.07 2 B44
thiophen-2-yl 4.07 682.96 2 B45 2-methylsulfanylpyridin-3-yl 4.1
723.99 2 B46 5-methyl-3-phenylisoxazol-4-yl 4.39 758.06 2 B47
4-methyl-2-phenylthiazol-5-yl 4.6 774.06 2 B48
5-pyridin-2-ylthiophen-2-yl 4.22 760.02 2 B49 5-phenylfuran-2-yl
4.54 743.02 2 B50 5-methyl-1-phenyl-1H-pyrazol-4-yl 4.17 757.06 2
B51 6-morpholin-4-yl-pyrazin-2-yl 4.03 763.92 2 B52
5-bromofuran-2-yl 4.26 744.84 2 B53 pyridin-2-yl 4.46 677.9 2 B54
pyridin-4-yl 3.57 677.9 2 B55 N-oxopyridin-3-yl 3.23 693.91 2 B56
pyrazin-2-yl 4.03 678.91 2 B57 3-bromothiophen-2-yl 4.84 760.8 2
B58 2,5-dimethylfuran-3-yl 4.29 694.91 2 B61 5-nitrofuran-2-yl 4.03
711.88 2 B62 2-chloro-5-nitrophenyl 4.29 755.9 2 B63
2,5-dimethylfuran-3-yl 4.36 775.84 2 B64 2-nitro-4-chlorophenyl
4.26 755.91 2 B65 3-methyl-4-bromophenyl 4.54 768.9 2 B66
3-chloropyridin-4-yl 3.87 711.91 2 B67 5-chlorothiophen-2-yl 4.36
716.85 2 B68 3-chloro-5-iodophenyl 4.55 836.84 2 B69
2-methyl-3-nitrophenyl 4.11 735.96 2 B70
3-chloro-5-trifluoromethylphenyl 4.42 778.92 2 B71 pyrimidin-2-yl
3.76 678.91 2 B72 2-chloro-5-methylphenyl 4.39 724.9 2 B73
2-chloro-4,5-difluorophenyl 4.33 746.88 2 B74
2-nitro-5-methylphenyl 4.13 735.94 2 B75
2,6-dichloro-5-fluoropyridin-3-yl 4.37 763.86 2 B76
4-bromo-2-ethyl-5-methyl-2H-pyrazol-3-yl 4.59 786.91 2 B77
4-fluoro-3-nitrophenyl 4.13 739.92 2 B78 2-pyridin-3-ylthiazol-4-yl
4.26 760.91 2 B80 2-nitrophenyl 4.04 721.9 2 B81
2-trifluoromethylpyridin-3-yl 3.97 745.92 2 B82
3-methylpyridin-4-yl 3.45 691.94 2 B83 5-bromo-2-chlorophenyl 4.52
788.81 2 B84 3-bromo-4-methylphenyl 4.52 768.87 2 B85
2-bromo-3-nitrophenyl 4.13 799.85 2 B86 2-methyl-3,5-dinitrophenyl
4.24 780.97 2 B87 3-methyl-2-nitrophenyl 4.11 735.9 2 B88
3-methylthiophen-2-yl 4.31 696.87 2 B89 3-methoxyisoxazol-5-yl 4.04
697.88 2 B90 6-chloro-1-oxypyridin-2-yl 4.12 727.89 2 B91
2-hydroxy-3,5-trichlorophenyl 4.2 760.84 2 B92
1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl 4.46 748.9 2 B93
3-chloro-2-methylpyridin-4-yl 3.98 725.88 2 B94 4-methyloxazol-5-yl
3.85 681.88 2 B95 2-methoxymethyl-4-methylthiazol-5-yl 4.02 741.93
2 B96 2,4-dimethylthiazol-5-yl 3.96 711.91 2 B97
2,6-dichloropyridin-4-yl 4.4 745.84 2 B98 3-methylisothiazol-4-yl
3.88 697.88 2 B99 2-methyl-3-carboxylic acid methyl 4.28 794.94 2
ester-4-methylsulfanylphenyl B100 1,5-dimethyl-1H-pyrazol-3-yl 4.15
694.9 2 B101 2-chloro-6-nitrophenyl 4.16 755.86 2 B102
4-chloro-2-fluoro-5-nitrophenyl 4.33 773.92 2 B103
4-chloro-5-difluoromethoxy-1-methyl- 4.4 780.87 2 1H-pyrazol-3-yl
B104 4-methyl-2-trifluoromethylthiazol-5-yl 4.42 765.87 2 B105
2-chloro-4-methylthiazol-5-yl 4.36 731.83 2 B106
2,3-dichloro-4-(2-methoxy- 4.38 818.88 2 ethoxy)phenyl B107
5-cyano-6-methylpyridin-2-yl 4.45 716.9 2 B108
2-methanesulfonyl-4-trifluoromethylphenyl 4.13 822.89 2 B109
2,4-dichloro-3-methoxyphenyl 4.46 774.84 2 B110 3-cyanomethylphenyl
3.95 715.89 2 B111 pyrimidin-5-yl 3.55 678.85 2 B112
5-tert-butyl-2-methyl-2H-pyrazol-3-yl 4.41 736.95 2 B113
2-methyl-5-trifluoromethyl-2H-pyrazol-3-yl 4.29 748.9 2 B114
2-chloro-4-methanesulfonyl-3-methoxyphenyl 4.03 818.87 2 B115
3-chloro-2-trifluoromethyl-pyridin-4-yl 4.3 779.85 2 B116
4-methylsulfanyl-2-nitrophenyl 4.2 767.85 2 B117
3-cyano-1-methyl-1H-pyrazol-4-yl 3.82 705.98 2 B118
2-(2-chlorophenyl)-4-trifluoromethyl- 4.85 861.85 2 thiazol-5-yl
B119 4-methanesulfonyl-3-methoxymethyl- 3.91 812.93 2
2-methylphenyl B120 3-[diethoxyphosphinyl)oxy]Phenyl 4.09 828.93 2
B121 2-isopropylsulfanylpyridin-3-yl 4.44 751.93 2 B122
2-(3-ethoxypropyl)-6-trifluoromethyl- 4.48 831.96 2 pyridin-3-yl
B123 4'-chloro-4-methylbiphenyl-3-yl 4.81 800.91 2 B124
thiophen-3-yl 4.02 682.83 2 B125
2-methylsulfanyl-4-trifluoromethylphenyl 4.48 790.86 2 B126
4-trifluoromethylpyridin-5-yl 3.96 745.86 2 B127
2-methyl-6-trifluoromethylpyridin-3-yl 4.19 759.89 2 B128
2,6-dichloronicotin-3-yl 4.31 745.8 2 B129
6-methoxy-3-bromo-2-methylphenyl 4.49 798.83 2 B130
2-chloro-4-fluoro-5-nitrophenyl 4.31 773.84 2 B131
3-difluoromethyl-1-methyl-1H-pyrazol-4-yl 3.9 730.88 2 B132
2-methoxypyridin-3-yl 4.47 707.87 2 B133
4-chloro-2-methyl-5-trifluoromethyl- 4.64 782.84 2 2H-pyrazol-3-yl
B134 2-methyl-4-trifluoromethylthiazol-5-yl 4.19 765.83 2 B135
2-chloro-4-bromophenyl 4.55 788.8 2 B136
4-chloro-1-methyl-5-trifluoromethyl- 4.56 782.84 2 1H-pyrazol-3-yl
B137 5-methylthiophen-2-yl 4.2 696.82 2 B138 4-bromo-2-methylphenyl
4.44 768.8 2 B139 4-bromo-3-methoxy-2-methylphenyl 4.42 798.83 2
B140 5-tert-butyl-2-methoxyphenyl 4.92 762.94 2 B141
3-chloro-5-trifluoromethylpyridin-2-yl 4.57 779.82 2 B142
5-chloro-1,3-dimethyl-1H-pyrazol-4-yl 4.14 728.85 2 B143
4,5-dichloroisothiazol-3-yl 4.63 751.75 2 B144
5-methyl-2-trifluoromethylfuran-3-yl 4.36 748.83 2 B145
3-chlorothiophen-2-yl 4.61 716.78 2 B146
2-chloro-6-methoxypyridin-4-yl 4.32 741.83 2 B147
5-chloro-4-methoxythiophen-3-yl 4.62 746.8 2 B148
2-fluoro-5-nitrophenyl 4.34 739.85 2 B149
3-chloro-2-fluoro-6-trifluoromethylphenyl 4.48 796.81 2 B150
6-difluoromethyl-2-methoxymethylpyridin- 4.09 771.9 2 3-yl B151
2-fluoropyridin-4-yl 3.88 695.84 2 B152
1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl 4.02 748.85 2 B153
2,5-difluorophenyl 4.1 712.93 2 B154 2-chloro-5-fluorophenyl 4.19
728.91 2 B155 2,4-dichlorophenyl 4.39 744.89 2 B156
2-methyl-3-chlorophenyl 4.39 724.89 2 B157
3,5-dimethyl-isoxazol-4-yl 3.96 695.86 2 B158 2,6-dichlorophenyl
116 B159 2-chloro-4-bromo-6-methylphenyl 114 B160
2-hydroxyl-3,5-dichloroPhenyl 200 B161
2-iodo-3-methyl-4-nitrophenyl 175 B162
2-bromo-3-methyl-4-nitrophenyl 172 B163
2-chloro-3-methyl-4-nitrophenyl 127 B164 2,6-dimethoxyphenyl 105
B165 3,5-dimethyl-4-nitrophenyl 218 B166 2-methoxy-6-fluorophenyl
112 B167 2-fluoro-4-trifluoromethylphenyl 183 B168
3,5-difluorophenyl 83 B169 2,5-difluorophenyl 154 B170
3-chloro-4-nitrophenyl 95 B171 3-acetate-4-nitrophenyl 100 B172
2,6-difluorophenyl 177 B173 3-ethoxy-4-nitrophenyl 238 B174
3-amino-4-nitrophenyl 205 B175 3-(N,N-dimethylamino)-4-nitrophenyl
181 B176 2,6-difluoro-4-cyanophenyl 214 B177
2-methoxy-4-nitrophenyl 190 B178 2-trifluoromethyl--4-nitrophenyl
140 B179 3-trifluoromethyl-4-nitrophenyl 142 B180 2,4-dinitrophenyl
246 B181 3-hydroxyl-4-nitrophenyl 185 B182 2-chloro-4-methylphenyl
172 B183 2-chloro-3-nitrophenyl 123 B184 2,3-dichlorophenyl 136
B185 3,5-dichloropyridin-2-yl 181 B186 2,5-dichlorothiophen-3-yl
188 B187 5-bromopyrimidin-2-yl 204 B188
3-trifluoromethylpyridin-2-yl 175 B189 2,4,6-trifluorophenyl 179
B190 3-methyl-4-nitrophenyl 107 B191 2-fluoro-4-nitrophenyl 212
B192 3-fluoro-4-nitrophenyl 104 B193 3-nitrophenyl 98 B194
2-fluoro-pyridin-3-yl 167 B195 3,4-dinitrophenyl 114 B196
2-methyl-4-nitrophenyl 104 B197 2-fluoro-4-nitrophenyl 199 B198
2-chloro-4-cyanophenyl 211 B202 2-chloro-pyridin-3-yl 2.05 710 4
B203 2-methoxy-4-cyano-6-hydroxyphenyl 2.1 599 4 B204
4-cyano-pyridin-3-yl 2.04 701 4 B205 3-fluoro-4-cyanophenyl 2.19
826 3 B206 3-bromo-4-cyanophenyl 2.18 778 3 B207
3-methoxy-4-nitrophenyl 2.12 750 4 B208 5-cyanopyridin-2-yl 208-210
B209 4-bromo-2,6-dichlorophenyl 250 B210 2,4-dichloropyrimidin-5-yl
114-115 B211 2,4-dichloro-6-methylphenyl 113-118 B212
2-methyl-4-fluoro-5-nitrophenyl 83-84 B213
2-methyl-4-cyano-5-5-nitrophenyl 158-161
TABLE-US-00007 TABLE C (Ic) ##STR00027## Comp. RT LC-MS No. Q.sup.1
(min) MH.sup.+ Method C1 2-chloro-4-fluorophenyl 2.19 686.7 1 C2
4-cyano-2-methylphenyl -- -- C3 2-fluorophenyl 2.24 650.8 1 C4
2-methylphenyl 2.16 646.8 1 C5 2-chlorophenyl 2.17 666.7 1 C6
4-cyanophenyl 2.05 657.8 1 C7 4-nitrophenyl 2.05 677.9 1 C8
4-methylphenyl 2.2 646.8 1 C9 4-fluoro-2-methylphenyl 2.18 664.8 1
C10 5-chloro-2-fluorophenyl 2.34 686.7 1 C11 2-chloro-4-nitrophenyl
2.16 713.7 1 C12 furan-2-yl 2.05 622.8 1 C13
4-trifluoromethoxyphenyl 2.28 716.8 1 C14
4-fluoro-3-trifluoromethyl- 2.27 718.8 1 phenyl C15
4-trifluoromethylphenyl 2.05 700.8 1 C16 2-trifluoromethoxyphenyl
2.26 716.8 1 C17 2-methoxyphenyl 2.27 662.8 1 C18 phenyl 2.12 634.7
1 C19 4-fluorophenyl 2.13 650.8 1 C20 2-trifluoromethylphenyl 2.17
700.7 1 C21 4-methyl-1,2,3-thiadiazol-5-yl 2.04 654.7 1 C22
2,3-difluorophenyl 2.24 668.7 1 C23 2,4-difluorophenyl 2.25 668.7 1
C24 2-fluoro-5-trifluoromethylphenyl 2.34 718.7 1 C25
2-methyl-4-nitrophenyl 2.15 690 3 C26 2,4-dichlorophenyl 2.22 699 3
C27 2,3-dichlorophenyl 2.2 699 3 C28 3-nitrophenyl 2.13 676 3 C29
2-chloropyridine-3-yl 2.07 666 3 C30 3,5-dimethylisoxazol-4-yl 2.09
650 3 C31 2-fluoro-4-cyanophenyl 2.14 674 3 C32
2-methyl-3-chlorophenyl 2.21 679 3 C33 2,4,6-trifluorophenyl 2.15
685 3 C34 2-fluoropyridin-3-yl 2.12 650 3 C35
3-methyl-4-nitrophenyl 2.17 690 3 C36 2-fluoro-4-nitrophenyl 2.17
694 3 C37 3-fluoro-4-nitrophenyl 2.14 694 3 C38 3,4-dinitrophenyl
2.14 721 3 C39 3-hydroxy-4-nitrophenyl 2.11 692 3 C40
2-chloro-4-cyanophenyl 2.13 690 3 C41 3-fluoro-4-cyanophenyl 2.12
674 3 C42 4-fluoro-3-cyanophenyl 2.11 674 3 C43
2-chloro-4-methylphenyl 2.21 679 3 C44 2-chloro-3-nitrophenyl 2.14
710 3
TABLE-US-00008 TABLE D (Id) ##STR00028## Comp. RT LC-MS No. Q.sup.1
R.sup.1 (min) MH.sup.+ Method D1 phenyl Me 3.92 646.98 2 D2 phenyl
Et 4.07 660.95 2 D3 4-cyanophenyl Me 3.8 671.94 2 D4 4-cyanophenyl
Et 3.96 685.97 2 D5 4-fluoro-2chlorophenyl Me 4.1 698.9 2 D6
4-fluoro-2chlorophenyl Et 4.23 712.87 2 D7 2-fluorophenyl Me 3.94
664.88 2 D8 2-methylphenyl Me 4.02 660.96 2 D9 2-chlorophenyl Me
4.05 682.92 2 D10 4-methylphenyl Me 4.06 660.97 2 D11
4-fluoro-2-methylphenyl Me 4.04 678.96 2 D12
5-chloro-2-fluorophenyl Me 4.13 698.93 2 D13 2-chloro-4-nitrophenyl
Me 4.08 725.94 2 D14 furan-2-yl Me 3.75 636.92 2 D15
4-trifluoromethoxyphenyl Me 4.26 730.94 2 D16
4-fluoro-3-trifluoromethyl- Me 4.23 732.95 2 phenyl D17
4-trifluoromethylphenyl Me 4.19 714.95 2 D18
2-trifluoromethoxyphenyl Me 4.21 730.94 2 D19 2-methoxyphenyl Me
3.9 676.97 2 D2 4-fluorophenyl Me 3.95 664.96 2 D21
2-trifluoromethylphenyl Me 4.15 714.95 2 D22
4-methyl-1,2,3-thiadiazol-5-yl Me 3.79 668.94 2 D23
2,3-difluorophenyl Me 3.97 682.94 2 D24 2,4-difluorophenyl Me 4.01
682.96 2 D25 2-fluoro-5-trifluoromethyl- Me 4.22 732.95 2 phenyl
D26 2-fluorophenyl Et 4.1 678.97 2 D27 2-methylphenyl Et 4.17
674.99 2 D28 2-chlorophenyl Et 4.18 694.94 2 D29 4-methylphenyl Et
4.2 674.99 2 D30 4-fluoro-2-methylphenyl Et 4.19 692.99 2 D31
5-chloro-2-fluorophenyl Et 4.29 712.94 2 D32 2-chloro-4-nitrophenyl
Et 4.22 739.84 2 D33 furan-2-yl Et 3.93 650.95 2 D34
4-trifluoromethoxyphenyl Et 4.4 744.96 2 D35
4-fluoro-3-trifluoromethyl- Et 4.34 746.92 2 phenyl D36
4-trifluoromethylphenyl Et 4.34 728.93 2 D37
2-trifluoromethoxyphenyl Et 4.34 744.91 2 D38 2-methoxyphenyl Et
4.05 690.93 2 D39 4-fluorophenyl Et 4.11 678.95 2 D40
2-trifluoromethylphenyl Et 4.26 728.92 2 D41 2,3-difluorophenyl Et
4.14 696.89 2 D42 2,4-difluorophenyl Et 4.14 696.89 2 D43
2-fluoro-5-trifluoromethylphenyl Et 4.34 746.92 2 D44
2-chloro-4-cyanophenyl Me 2.11 704 4 D45 2-chloro-4-cyanophenyl Et
2.13 718 4 D46 4-nitrophenyl Me 2.1 690 4 D47 4-nitrophenyl Et 2.15
704 4 D48 2,6-difluorophenyl Me 2.12 681 4 D49 2,6-difluorophenyl
Et 2.17 696 4
TABLE-US-00009 TABLE E (Ie) ##STR00029## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method E1 2-fluorophenyl 4.27
600.78 2 E2 2-methylphenyl 4.13 596.83 2 E3 2-chlorophenyl 4.11
616.78 2 E4 4-cyanophenyl 3.87 607.81 2 E5 4-nitrophenyl 4.06
627.82 2 E6 4-methylphenyl 4.17 596.86 2 E7 4-fluoro-2-methylphenyl
4.12 614.83 2 E8 5-chloro-2-fluorophenyl 4.46 634.78 2 E9
2-chloro-4-nitrophenyl 4.19 661.78 2 E10 furan-2-yl 3.87 572.85 2
E11 4-trifluoromethoxyphenyl 4.35 666.82 2 E12
4-fluoro-3-trifluoromethyl- 4.31 668.82 2 phenyl E13
4-trifluoromethylphenyl 4.3 650.85 2 E14 2-trifluoromethoxyphenyl
4.3 666.87 2 E15 2-methoxyphenyl 4.29 612.87 2 E16 phenyl 4 582.87
2 E17 4-fluorophenyl 4.04 600.85 2 E18 2-trifluoromethylphenyl 4.13
650.88 2 E19 2-chloro-4-fluorophenyl 4.16 634.82 2 E20
4-methyl-1,2,3-thiadiazol-5-yl 3.81 604.82 2 E21 2,3-difluorophenyl
4.24 618.85 2 E22 2,4-difluorophenyl 4.31 618.85 2 E23
2-fluoro-5-trifluoromethyl- 4.48 668.86 2 phenyl E24
2,5-difluoro-4-cyanophenyl 192 E25 2-methyl-4-cyanophenyl 2.08 620
4 E26 3-methyl-4-nitrophenyl 2.13 640 4 E27 2-methyl-4-nitrophenyl
2.11 640 4 E28 2,4,6-trifluorophenyl 2.11 635 4 E29
2,6-difluorophenyl 2.09 617 4
TABLE-US-00010 TABLE F (If) ##STR00030## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method F1 2-fluorophenyl 4.2
610.92 2 F2 2-methylphenyl 4.05 606.96 2 F3 2-chlorophenyl 4.07
626.9 2 F4 furan-2-yl 3.85 582.98 2 F5 4-trifluoromethoxyphenyl 4.3
676.94 2 F6 3-trifluoromethyl-4- 4.28 678.96 2 fluorophenyl F7
4-methyl-1,2,3-thiadiazol- 3.8 614.95 2 5-yl F8 2,3-difluorophenyl
4.2 628.96 2 F9 2,4-difluorophenyl 4.23 628.97 2 F10
2,4,6-trimethylphenyl 4.29 635.03 2 F11 2,3-dimethylphenyl 4.17
621.05 2 F12 2-fluoro-5-chlorophenyl 4.42 644.97 2 F13
2-fluoro-4-chlorophenyl 4.42 644.97 2 F14
2-fluoro-4-trifluoromethyl- 4.43 679 2 phenyl F15
2,4-dichlorophenyl 4.29 660.95 2 F16 2-chloro-4-methane- 3.78
704.95 2 sulfonylphenyl F17 3,4-dichlorophenyl 4.38 660.91 2 F18
4-methanesulfonylphenyl 3.64 670.96 2 F19 4-chlorophenyl 4.19
626.97 2 F20 3-fluorophenyl 4.05 611 2 F21 3-cyanophenyl 3.9 618 2
F22 3-methoxyphenyl 4.03 623 2 F23 3-methyl-4-nitrophenyl 179 F24
2-methyl-4-nitrophenyl 203 F25 2,4,6-trifluorophenyl 194 F26
4-trifluoromethylphenyl 163 F27 2-methyl-4-fluorophenyl 178 F28
2-chloro-4-nitrophenyl 207 F29 4-nitrophenyl 105 F30
2-chloro-4-fluorophenyl 164
TABLE-US-00011 TABLE G (Ig) ##STR00031## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method G1
2-methyl-4-cyanophenyl 190 G2 2-chloro-4-cyanophenyl 211 G3
2,4,6-trifluorophenyl 181 G4 2,6-difluoro-4-cyanophenyl 118 G5
2-chloro-4-fluorophenyl 4.23 679.1 183 2 G6 2-fluorophenyl 4.3
645.15 2 G7 2-methylphenyl 4.15 641.19 2 G8 2-chlorophenyl 4.17
661.13 2 G9 4-cyanophenyl 3.93 652.17 2 G10 4-nitrophenyl 4.08
672.14 2 G11 4-methylphenyl 4.23 641.19 2 G12
4-fluoro-2-methylphenyl 4.19 659.17 2 G13 5-chloro-2-fluorophenyl
4.52 679.12 2 G14 2-chloro-4-nitrophenyl 4.2 706.1 2 G15 furan-2-yl
3.94 617.14 2 G16 4-trifluoromethoxyphenyl 4.41 711.11 2 G17
4-fluoro-3-trifluoromethyl- 4.4 713.12 2 phenyl G18
4-trifluoromethylphenyl 4.36 695.12 2 G19 2-trifluoromethoxyphenyl
4.37 711.11 2 G20 2-methoxyphenyl 4.43 657.17 2 G21 phenyl 4.07
627.15 2 G22 4-fluorophenyl 4.09 645.15 2 G23
2-trifluoromethylphenyl 4.18 695.12 2 G24
4-methyl-1,2,3-thiadiazol-5-yl 3.88 649.12 2 G25 2,3-difluorophenyl
4.3 663.15 2 G26 2,4-difluorophenyl 4.34 663.15 2 G27
2-fluoro-5-trifluoromethyl- 4.54 713.12 2 phenyl
TABLE-US-00012 TABLE H (Ih) ##STR00032## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method H1
2-methyl-4-cyanophenyl 110 H2 2,4,6-trifluorophenyl 138 H3
2-fluorophenyl 4.44 661.33 2 H4 2-methylphenyl 4.32 657.37 2 H5
2-chlorophenyl 4.33 677.32 2 H6 4-cyanophenyl 4.12 668.35 2 H7
4-nitrophenyl 4.22 688.35 2 H8 4-methylphenyl 4.38 657.24 2 H9
4-fluoro-2-methylphenyl 4.35 675.36 2 H10 5-chloro-2-fluorophenyl
4.68 695.29 2 H11 2-chloro-4-nitrophenyl 4.34 722.28 2 H12
furan-2-yl 4.13 633.33 2 H13 4-trifluoromethoxyphenyl 4.55 727.29 2
H14 4-fluoro-3-trifluoromethyl- 4.51 729.3 2 phenyl H15
4-trifluoromethylphenyl 4.5 711.3 2 H16 2-trifluoromethoxyphenyl
4.53 727.32 2 H17 2-methoxyphenyl 4.52 673.35 2 H18 phenyl 4.2
643.27 2 H19 4-fluorophenyl 4.24 661.27 2 H20
2-trifluoromethylphenyl 4.34 711.3 2 H21
4-methyl-1,2,3-thiadiazol-5-yl 4.04 665.3 2 H22 2,3-difluorophenyl
4.48 679.32 2 H23 2,4-difluorophenyl 4.48 679.29 2 H24
2-fluoro-5-trifluoromethyl- 4.66 729.3 2 phenyl H25
2-chloro-4-fluorophenyl 4.39 695.26 98 2
TABLE-US-00013 TABLE I (Ii) ##STR00033## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method I1
2-methyl-4-cyanophenyl 130 -- I2 2,4,6-trifluorophenyl 190 -- I3
2-fluorophenyl 4.47 705.3 2 I4 2-methylphenyl 4.3 701.3 2 I5
2-chlorophenyl 4.33 721.2 2 I6 4-cyanophenyl 4.18 712.3 2 I7
4-nitrophenyl 4.22 732.3 2 I8 4-methylphenyl 4.39 701.29 2 I9
4-fluoro-2-methylphenyl 4.39 719.29 2 I10 5-chloro-2-fluorophenyl
4.66 739.24 2 I11 2-chloro-4-nitrophenyl 4.5 766.26 2 I12
furan-2-yl 4.12 677.26 2 I13 4-trifluoromethoxyphenyl 4.55 771.28 2
I14 4-fluoro-3-trifluoromethyl- 4.51 773.29 2 phenyl I15
4-trifluoromethylphenyl 4.5 755.29 2 I16 2-trifluoromethoxyphenyl
4.54 771.28 2 I17 2-methoxyphenyl 4.52 717.34 2 I18 phenyl 4.23
687.32 2 I19 4-fluorophenyl 4.24 705.32 2 I20
2-trifluoromethylphenyl 4.34 755.29 2 I21
4-methyl-1,2,3-thiadiazol-5-yl 4.05 709.29 2 I22 2,3-difluorophenyl
4.45 723.27 2 I23 2,4-difluorophenyl 4.5 723.31 2 I24
2-fluoro-5-trifluoromethyl- 4.68 773.29 2 phenyl I25
2-chloro-4-fluorophenyl 4.4 739.26 113 2
TABLE-US-00014 TABLE J (Ij) ##STR00034## Comp. RT MP LC-MS No.
Q.sup.1 (min) MH.sup.+ (.degree. C.) Method J1
2-chloro-4-cyanophenyl 110 J2 2,6-difluoro-4-cyanophenyl 113 J3
2,4,6-trifluorophenyl 96 J4 2-methyl-4-cyanophenyl 102 J5
2-fluorophenyl 4.34 575.36 2 J6 2-methylphenyl 4.16 571.33 2 J7
2-chlorophenyl 4.15 591.35 2 J8 4-cyanophenyl 3.99 582.38 2 J9
4-nitrophenyl 4.07 602.36 2 J10 4-methylphenyl 4.22 571.4 2 J11
4-fluoro-2-methylphenyl 4.19 589.4 2 J12 5-chloro-2-fluorophenyl
4.52 609.32 2 J13 2-chloro-4-nitrophenyl 4.23 636.31 2 J14
furan-2-yl 3.95 547.36 2 J15 4-trifluoromethoxyphenyl 4.41 641.32 2
J16 4-fluoro-3-trifluoromethyl- 4.4 643.33 2 phenyl J17
4-trifluoromethylphenyl 4.37 625.33 2 J18 2-trifluoromethoxyphenyl
4.38 641.32 2 J19 2-methoxyphenyl 4.37 587.38 2 J20 phenyl 4.08
557.36 2 J21 4-fluorophenyl 4.08 575.36 2 J22
2-trifluoromethylphenyl 4.19 625.33 2 J23
4-methyl-1,2,3-thiadiazol-5-yl 3.87 579.33 2 J24 2,3-difluorophenyl
4.33 593.36 2 J25 2,4-difluorophenyl 4.34 593.36 2 J26
2-fluoro-5-trifluoromethyl- 4.54 643.33 2 phenyl J27
2-chloro-4-fluorophenyl 4.23 609.29 88 2
TABLE-US-00015 TABLE K (Ik) ##STR00035## Comp. MP No. Q.sup.1
(.degree. C.) K1 2,4,6-trifluorophenyl 173 K2 4-nitrophenyl 190 K3
2-chloro-4-cyanohenyl 133 K4 2-methyl-4-cyanophenyl 152
TABLE-US-00016 TABLE L (IL) ##STR00036## Comp. RT LC-MS No. Q.sup.1
(min) MH.sup.+ Method L1 2-fluorophenyl 4.34 639.5 2 L2
2-methylphenyl 4.2 635.53 2 L3 2-chlorophenyl 4.21 655.45 2 L4
4-cyanophenyl 4.01 646.52 2 L5 4-nitrophenyl 4.11 666.48 2 L6
4-methylphenyl 4.26 635.52 2 L7 4-fluoro-2-methylphenyl 4.23 653.23
2 L8 5-chloro-2-fluorophenyl 4.53 673.43 2 L9
2-chloro-4-nitrophenyl 4.22 700.45 2 L10 furan-2-yl 3.98 611.52 2
L11 4-trifluoromethoxyphenyl 4.43 705.51 2 L12
4-fluoro-3-trifluoromethyl- 4.4 707.51 2 phenyl L13
4-trifluoromethylphenyl 4.38 689.52 2 L14 2-trifluoromethoxyphenyl
4.4 705.29 2 L15 2-methoxyphenyl 4.41 651.52 2 L16 phenyl 4.1 621.4
2 L17 4-fluorophenyl 4.13 639.5 2 L18 2-trifluoromethylphenyl 4.22
689.51 2 L19 2-chloro-4-fluorophenyl 4.25 673.48 2 L20
4-methyl-1,2,3-thiadiazol-5-yl 3.93 643.46 2 L21 2,3-difluorophenyl
4.33 657.02 2 L22 2,4-difluorophenyl 4.36 657.51 2 L23
2-fluoro-5-trifluoromethyl- 4.55 707.51 2 phenyl
TABLE-US-00017 TABLE M (Im) ##STR00037## Comp. RT LC-MS No. Q1 R
(min) MH.sup.+ Method M1 2-methyl-4-cyanophenyl Et 2.14 742 4 M2
3-methyl-4-nitrophenyl Et 2.17 762 4
Biological Examples
[0216] These Examples illustrate the insecticidal and acaricidal
properties of the compounds of formula (I). The tests were
performed as follows: Spodoptera littoralis (Egyptian Cotton
Leafworm): Cotton leaf discs were placed on agar in a 24-well
microtiter plate and sprayed with test solutions at an application
rate of 200 ppm. After drying, the leaf discs were infested with 5
L1 larvae. The samples were checked for mortality, feeding
behavior, and growth regulation 3 days after treatment (DAT). The
following compound gave at least 80% control of Spodoptera
littoralis: A1 to A22, B202 to B207, B188, B187, B186, B185, B159,
B158, B152, B151, B150, B166, B148, B147, B146, B144, B142, B141,
B139, B138, B137, B135, B134, B131, B130, B128, B127, B126, B124,
B120, B117, B116, B115, B114, B113, B112, B111, B110, B109, B105,
B104, B102, B101, B100, B99, B98, B97, B96, B95, B94, B93, B92,
B89, B88, B87, B86, B85, B84, B82, B81, B83, B80, B77, B74, B73,
B72, B71, B70, B69, B68, B67, B66, B65, B64, B62, B61, B58, B56,
B55, B54, B52, B48, B45, B44, B42, B39, B37, B36, B32, B31, B30,
B28, B27, B26, B25, B175, B174, B176, B170, B169, B168, B167, B154,
B172, B153, B180, B179, B178, B182, B184, B183, B156, B195, B194,
B193, B155, B192, B191, B190, B189, B157, B198, B197, B196, B24,
B23, B22, B21, B20, B19, B18, B17, B16, B15, B14, B13, B12, B11,
B10, B9, B8, B7, B6, B5, B4, B3, B2, B1, C1 to C15, C18 to C23, C25
to C36, D1 to D13, D15, D17, D20, D23, D22, D26 to D30, D32 to D36,
D39 to D42, D44 to D49, E1 to E22, E24, E25 to E29, F1 to F9, F12,
F13, F15 to F30, G1 to G5, K1 to K4, M1, M2. Heliothis virescens
(Tobacco Budworm): Eggs (0-24 h old) were placed in 24-well
microtiter plate on artificial diet and treated with test solutions
at an application rate of 200 ppm (concentration in well 18 ppm) by
pipetting. After an incubation period of 4 days, samples were
checked for egg mortality, larval mortality, and growth regulation.
The following compound gave at least 80% control of Heliothis
virescens: A1, A4, A6 to A21, B202 to B207, B188, B185, B163, B162,
B161, B159, B158, B152, B151, B150, B166, B148, B146, B144, B141,
B139, B138, B137, B135, B134, B131, B130, B128, B127, B126, B125,
B124, B120, B117, B116, B115, B114, B113, B112, B111, B110, B109,
B104, B102, B101, B100, B99, B98, B97, B96, B95, B94, B93, B89,
B88, B87, B86, B85, B84, B82, B81, B83, B80, B77, B74, B73, B72,
B70, B69, B68, B67, B66, B65, B64, B62, B61, B58, B56, B55, B52,
B48, B45, B44, B42, B39, B36, B32, B31, B30, B27, B26, B25, B175,
B174, B176, B171, B170, B169, B168, B167, B172, B153, B180, B179,
B178, B182, B184, B183, B156, B195, B194, B193, B155, B192, B191,
B190, B189, B157, B198, B197, B23, B22, B21, B20, B19, B18, B17,
B15, B13, B12, B11, B10, B9, B8, B7, B6, B5, B4, B3, B2, B1, C1 to
C23, C25 to C29, C31 to C35, D1 to D7, D10 to D13, D15, D16, D20,
D22 to D24, D26, D28 to D30, D32, D35, D36, D39 to D42, D44 to D49,
E1 to E24, E25 to E29, F1 to F9, F12, F13, F15 to F30, G1 to G5,
H1, H2, H25, I1, I2, I25, J2 to J4, J27, K1 to K4, M1, M2. Plutella
xylostella (Diamond Back Moth): 24-well microtiter plate (MTP) with
artificial diet was treated with test solutions at an application
rate of 200 ppm (concentration in well 18 ppm) by pipetting. After
drying, the MTP's were infested with L2 larvae (7-12 per well).
After an incubation period of 6 days, samples were checked for
larval mortality and growth regulation. The following compound gave
at least 80% control of Plutella xylostella: A1, A2, A4 to A22,
B202 to B207, B187, B185, B164, B163, B162, B161, B160, B159, B158,
B152, B151, B150, B166, B148, B146, B144, B141, B139, B138, B137,
B135, B134, B131, B130, B128, B127, B126, B125, B124, B120, B117,
B116, B115, B114, B113, B112, B111, B110, B109, B105, B104, B102,
B101, B100, B99, B98, B97, B96, B95, B94, B93, B89, B88, B87, B86,
B85, B84, B82, B81, B83, B80, B77, B74, B73, B72, B71, B69, B67,
B66, B65, B64, B62, B61, B58, B57, B56, B55, B54, B52, B48, B45,
B44, B42, B39, B37, B36, B32, B31, B28, B27, B26, B25, B175, B174,
B176, B171, B170, B169, B168, B154, B172, B153, B180, B179, B178,
B182, B184, B183, B156, B195, B194, B193, B155, B192, B191, B190,
B189, B198, B197, B196, B23, B22, B21, B20, B19, B18, B16, B15,
B14, B13, B12, B11, B10, B9, B8, B7, B6, B5, B4, B3, B2, B1, C1 to
C9, C11 to C13, C15, C18 to C23, C25 to C29, C31 to C35, D1 to D13,
D15, D16, D20, D22 to D24, D26 to D30, D32, D36, D39 to D42, D44 to
D49, E4 to E22, E24, E25 to E29, F1 to F9, F11, F15 to F27, F29,
F30, G1 to G5, H1, H2, H25, I1, I2, I25, J1 to J4, J27, K1 to K4,
M1, M2. Diabrotica balteata (Corn Root Worm): A 24-well microtiter
plate (MTP) with artificial diet was treated with test solutions at
an application rate of 200 ppm (concentration in well 18 ppm) by
pipetting. After drying, the MTP's were infested with L2 larvae
(6-10 per well). After an incubation period of 5 days, samples were
checked for larval mortality and growth regulation. The following
compound gave at least 80% control of Diabrotica balteata: A1, A3
to A13, A15 to A20, A22, B202 to B206, B187, B185, B163, B162,
B161, B159, B158, B151, B150, B166, B146, B144, B137, B135, B134,
B131, B130, B128, B127, B126, B125, B120, B117, B116, B115, B113,
B112, B111, B110, B109, B101, B100, B98, B97, B96, B93, B92, B89,
B87, B86, B85, B84, B82, B81, B83, B80, B74, B73, B72, B69, B67,
B66, B64, B62, B61, B58, B56, B55, B54, B52, B45, B44, B42, B37,
B36, B32, B30, B28, B27, B26, B25, B174, B170, B169, B168, B167,
B154, B153, B180, B179, B178, B181, B184, B183, B156, B194, B155,
B192, B22, B21, B20, B18, B9, B5, B4, B3, C1 to C13, D15, C19 to
C23, C25 to C29, C31 to C36, D1 to D13, D15 to D17, D20 to D23, D26
to D30, D32, D36, D39, D42, D41, D44 to D49, E1 to E7, E8, E9, E11,
E13, E16 to E22, E24, E25 to E29, F1, F3, F7 to F9, F12, F15 to
F23, F24 to F30, G1 to G5, H2, H25, 11, 12, 125, J1 to J4, J27, K1
to K4, M2. Thrips tabaci (Onion Thrips): Sunflower leaf discs were
placed on agar in a 24-well microtiter plate and sprayed with test
solutions at an application rate of 200 ppm. After drying, the leaf
discs were infested with an aphid population of mixed ages. After
an incubation period of 7 days, samples were checked for mortality.
The following compounds gave at least 80% control of Thrips tabaci:
A2 to A13, A11 to A20, A22, B202, B204, B163, B162, B161, B151,
B150, B146, B137, B135, B134, B127, B124, B115, B113, B112, B111,
B110, B109, B101, B97, B93, B92, B89, B87, B82, B81, B80, B74, B73,
B67, B66, B65, B64, B58, B55, B54, B52, B49, B46, B45, B44, B42,
B37, B36, B28, B27, B26, B25, B175, B174, B176, B169, B168, B167,
B154, B172, B153, B180, B178, B184, B183, B156, B155, B192, B191,
B190, B21, B20, B9, B4, B1, C1 to C9, C11, C13, C15, C18, C19, C20
to C23, C25, C26, C29, C31, C33, D1 to D5, D9, D12, D15, D17, D20,
D22, D23, D26 to D30, D32 to D36, D44 to D49, E1 to E7, E9, E11,
E12, E13, E16 to E22, E25, E27 to E29, F3, F7, F8, F20, F21, F29,
F30, H25, 12, 125, J27, K1, K2, M1. Tetranychus urticae
(Two-Spotted Spider Mite): Bean leaf discs on agar in 24-well
microtiter plates were sprayed with test solutions at an
application rate of 200 ppm. After drying, the leaf discs are
infested with mite populations of mixed ages. 8 days later, discs
are checked for egg mortality, larval mortality, and adult
mortality. The following compounds gave at least 80% control of
Tetranychus urticae: A2 to A7, A10, A11, A16 to A18, A22, B202,
B204, B159, B158, B151, B150, B139, B138, B135, B134, B128, B127,
B113, B111, B110, B109, B106, B104, B101, B98, B97, B96, B93, B82,
B81, B80, B74, B73, B69, B67, B66, B65, B64, B61, B55, B54, B42,
B36, B28, B26, B174, B176, B171, B170, B169, B168, B154, B172,
B153, B180, B179, B178, B184, B183, B156, B195, B194, B193, B155,
B192, B191, B190, B189, B198, B197, B196, B23, B21, B19, B15, B13,
B11, B9, B8, B7, B6, B5, B4, B2, B1, C2, C4 to C9, C11, C12, C13,
C15, C19 to C23, C25, C26, C29, C33, D2 to D6, D8, D11, D13, D20,
D22, D32, D39, D44 to D49, E4, E5, E7, E9, E12, E13, E17, E19, E20,
E24, E25, E27 to E29, F21, F18, F15, F7, F5, F1, F28, F27, F25,
F24, F29, F30, G1 to G5, J2, J27, K1 to K4, M1. Myzus persicae
(Green Peach Aphid): Sunflower leaf discs were placed on agar in a
24-well microtiter plate and sprayed with test solutions at an
application rate of 200 ppm. After drying, the leaf discs were
infested with an aphid population of mixed ages. After an
incubation period of 6 DAT, samples were checked for mortality. The
following compounds gave at least 80% control of Myzus persicae:
A3, A4, A10, A11, A13, A17, A18, A22, B204, B151, B150, B137, B124,
B111, B106, B98, B93, B89, B82, B80, B66, B55, B54, B45, B44, B42,
B37, B36, B28, B26, B174, B168, B153, B156, B155, B189, B19, B18,
B15, B8, B7, B6, B5, B4, B2, C1, C4 to C6, C8, C18, C19, D1 to D4,
D20, D21, D39, D45, D48, D49, E1, E2, E4 to E6, E9, E11, E12, E13,
E16, E17, E21, E25, E27 to E29, F7, F30, G3, G4, G5, H1, H25, 12,
125, J27, K2, K27.
* * * * *